Compositions containing one or more poly alpha-1,3-glucan ether compounds

ABSTRACT

Compositions comprising cellulase and at least one poly alpha-1,3-glucan ether compound having a degree of substitution with an organic group of about 0.05-3.0 are disclosed. Such compositions can be dry or aqueous, the latter of which can have a viscosity of at least about 10 cPs. The disclosed composition can be in the form of a personal care product, household product, or industrial product, for example. Also disclosed are a method for preparing an aqueous composition comprising cellulase and a poly alpha-1,3-glucan ether compound, and a method of treating a material such as fabric by contacting it with this aqueous composition.

This application claims the benefit of U.S. Provisional Application No.62/014,318 (filed Jun. 19, 2014), which is incorporated herein byreference in its entirety.

FIELD OF INVENTION

This invention is in the field of personal care, household products, andindustrial products. For example, this invention pertains tocompositions comprising cellulase and a poly alpha-1,3-glucan ethercompound.

BACKGROUND

Driven by a desire to find new structural polysaccharides usingenzymatic syntheses or genetic engineering of microorganisms or planthosts, researchers have discovered polysaccharides that arebiodegradable, and that can be made economically from renewableresource-based feedstocks. One such polysaccharide is polyalpha-1,3-glucan, a glucan polymer characterized by havingalpha-1,3-glycosidic linkages. This polymer has been isolated bycontacting an aqueous solution of sucrose with a glucosyltransferaseenzyme isolated from Streptococcus salivarius (Simpson et al.,Microbiology 141:1451-1460, 1995).

U.S. Pat. No. 7,000,000 disclosed the preparation of a polysaccharidefiber comprising hexose units, wherein at least 50% of the hexose unitswithin the polymer were linked via alpha-1,3-glycosidic linkages usingan S. salivarius gtfJ enzyme. This enzyme utilizes sucrose as asubstrate in a polymerization reaction producing poly alpha-1,3-glucanand fructose as end-products (Simpson et al., 1995). The disclosedpolymer formed a liquid crystalline solution when it was dissolved abovea critical concentration in a solvent or in a mixture comprising asolvent. From this solution continuous, strong, cotton-like fibers,highly suitable for use in textiles, were spun and used.

Modified cellulosic polymers have been used in detergent formulations toprovide a variety of benefits including anti-redeposition and fabriccare benefits (U.S. Pat. Nos. 7,012,053, 7,056,880, 6,579,840,7,534,759, 7,576,048). Some of these polymers have also been used toadjust the viscosity of the detergent formulation itself. However, lackof stability of cellulose-based polymers to cellulases is a majorlimitation for using these polymers in detergent formulations. Enzymesused in detergents often contain trace amounts of cellulase. Also,cellulase is generally included in detergent formulations to providecolor clarification and pill removal benefits. But the incompatibilityof cellulosic polymers and cellulase enzymes limits the use of thesecomponents together in a formulation.

SUMMARY OF INVENTION

In one embodiment, the disclosure concerns a composition comprising acellulase and a poly alpha-1,3-glucan ether compound represented by thestructure:

wherein(i) n is at least 6,(ii) each R is independently an H or an organic group, and(iii) the compound has a degree of substitution of about 0.05 to about3.0.

In a second embodiment, at least one organic group is selected from thegroup consisting of carboxy alkyl group, hydroxy alkyl group, and alkylgroup. At least one organic group is selected from the group consistingof carboxymethyl, hydroxypropyl, dihydroxypropyl, hydroxyethyl, methyl,and ethyl group in a third embodiment. The organic group is acarboxymethyl group in a fourth embodiment.

In a fifth embodiment, the composition is in the form of a personal careproduct, household product, or industrial product. The composition is afabric care product in a sixth embodiment.

In a seventh embodiment, the composition is an aqueous composition. Thecomposition has a viscosity of at least about 10 cPs in an eighthembodiment.

In a ninth embodiment, the disclosure concerns a method for preparing anaqueous composition. This method comprises contacting an aqueouscomposition with a poly alpha-1,3-glucan ether compound represented bythe structure:

wherein(i) n is at least 6,(ii) each R is independently an H or an organic group, and(iii) the compound has a degree of substitution of about 0.05 to about3.0. The aqueous composition prepared in this method comprises acellulase.

In a tenth embodiment, the cellulase is (i) comprised in the aqueouscomposition prior to the contacting step, or (ii) added to the aqueouscomposition during or after the contacting step.

In an eleventh embodiment, (i) the viscosity of the aqueous compositionis increased by the poly alpha-1,3-glucan ether compound, and/or (ii)the shear thinning behavior or the shear thickening behavior of theaqueous composition is increased by the poly alpha-1,3-glucan ethercompound.

In a twelfth embodiment, the disclosure concerns a method of treating amaterial. This method comprises contacting a material with an aqueouscomposition comprising a cellulase and a poly alpha-1,3-glucan ethercompound represented by the structure:

wherein(i) n is at least 6,(ii) each R is independently an H or an organic group, and(iii) the compound has a degree of substitution of about 0.05 to about3.0. The poly alpha-1,3-glucan ether compound can adsorb to the surfaceof the material in certain embodiments of this method.

In a thirteenth embodiment, the material comprises fabric. The fabriccomprises a (i) natural fiber, (ii) synthetic fiber, or a combination ofboth (i) and (ii), in a fourteenth embodiment. In a fifteenthembodiment, the poly alpha-1,3-glucan ether compound adsorbs to thefabric.

DETAILED DESCRIPTION OF INVENTION

The disclosures of all patent and non-patent literature cited herein areincorporated herein by reference in their entirety.

As used herein, the term “invention” or “disclosed invention” is notmeant to be limiting, but applies generally to any of the inventionsdefined in the claims or described herein. These terms are usedinterchangeably herein.

The terms “cellulase” and “cellulase enzyme” are used interchangeablyherein to refer to an enzyme that hydrolyzes beta-1,4-D-glucosidiclinkages in cellulose, thereby partially or completely degradingcellulose. Cellulase can alternatively be referred to as“beta-1,4-glucanase”, for example, and can have endocellulase activity(EC 3.2.1.4), exocellulase activity (EC 3.2.1.91), or cellobiaseactivity (EC 3.2.1.21). A cellulase in certain embodiments herein canalso hydrolyze beta-1,4-D-glucosidic linkages in cellulose etherderivatives such as carboxymethyl cellulose. “Cellulose” refers to aninsoluble polysaccharide having a linear chain of beta-1,4-linkedD-glucose monomeric units.

The terms “fabric”, “textile”, “cloth” and the like are usedinterchangeably herein to refer to a woven material having a network ofnatural and/or artificial fibers. Such fibers can be thread or yarn, forexample.

A “fabric care composition” herein is any composition suitable fortreating fabric in some manner. Examples of such a composition includelaundry detergents and fabric softeners.

The terms “heavy duty detergent”, “all-purpose detergent” and the likeare used interchangeably herein to refer to a detergent useful forregular washing of white and colored textiles at any temperature. Theterms “low duty detergent”, “fine fabric detergent” and the like areused interchangeably herein to refer to a detergent useful for the careof delicate fabrics such as viscose, wool, silk, microfiber or otherfabric requiring special care. “Special care” can include conditions ofusing excess water, low agitation, and/or no bleach, for example.

A “detergent composition” herein typically comprises at least asurfactant (detergent compound) and/or a builder. A “surfactant” hereinrefers to a substance that tends to reduce the surface tension of aliquid in which the substance is dissolved. A surfactant may act as adetergent, wetting agent, emulsifier, foaming agent, and/or dispersant,for example.

The terms “anti-redeposition agent”, “anti-soil redeposition agent”,“anti-greying agent” and the like herein refer to agents that help keepsoils from redepositing onto clothing in laundry wash water after thesesoils have been removed, therefore preventing greying/discoloration oflaundry. Anti-redeposition agents can function by helping keep soildispersed in wash water and/or by blocking attachment of soil ontofabric surfaces.

An “oral care composition” herein is any composition suitable fortreating an soft or hard surface in the oral cavity such as dental(teeth) and/or gum surfaces.

The term “adsorption” herein refers to the adhesion of a compound (e.g.,poly alpha-1,3-glucan ether) to the surface of a material.

The terms “poly alpha-1,3-glucan”, “alpha-1,3-glucan polymer”, “glucanpolymer” and the like are used interchangeably herein. Polyalpha-1,3-glucan is a polymer comprising glucose monomeric units linkedtogether by glycosidic linkages (i.e., glucosidic linkages), wherein atleast about 50% of the glycosidic linkages are alpha-1,3-glycosidiclinkages. Poly alpha-1,3-glucan is a type of polysaccharide. The term“alpha-1,3-glycosidic linkage” as used herein refers to the type ofcovalent bond that joins alpha-D-glucose molecules to each other throughcarbons 1 and 3 on adjacent alpha-D-glucose rings.

Poly alpha-1,3-glucan that can be used for preparing polyalpha-1,3-glucan ether compounds herein can be prepared using chemicalmethods. Alternatively, it can be prepared by extracting it from variousorganisms, such as fungi, that produce poly alpha-1,3-glucan.Alternatively still, poly alpha-1,3-glucan can be enzymatically producedfrom sucrose using one or more glucosyltransferase (gtf) enzymes (e.g.,gtfJ), such as described in U.S. Pat. No. 7,000,000, and U.S. PatentAppl. Publ. Nos. 2013/0244288 and 2013/0244287 (all of which areincorporated herein by reference), for example.

The terms “glucosyltransferase enzyme”, “gtf enzyme”, “gtf”,“glucansucrase” and the like are used interchangeably herein. Theactivity of a gtf enzyme herein catalyzes the reaction of the substratesucrose to make the products poly alpha-1,3-glucan and fructose. Otherproducts (byproducts) of a gtf reaction can include glucose (resultsfrom when glucose is hydrolyzed from the glucosyl-gtf enzymeintermediate complex), various soluble oligosaccharides (e.g., DP2-DP7),and leucrose (results from when glucose of the glucosyl-gtf enzymeintermediate complex is linked to fructose). Leucrose is a disaccharidecomposed of glucose and fructose linked by an alpha-1,5 linkage. Wildtype forms of glucosyltransferase enzymes generally contain (in theN-terminal to C-terminal direction) a signal peptide, a variable domain,a catalytic domain, and a glucan-binding domain. A gtf herein isclassified under the glycoside hydrolase family 70 (GH70) according tothe CAZy (Carbohydrate-Active EnZymes) database (Cantarel et al.,Nucleic Acids Res. 37:D233-238, 2009).

The terms “glycosidic linkage” and “glycosidic bond” are usedinterchangeably herein and refer to the type of covalent bond that joinsa carbohydrate (sugar) molecule to another group such as anothercarbohydrate. The term “alpha-1,3-glycosidic linkage” as used hereinrefers to the type of covalent bond that joins alpha-D-glucose moleculesto each other through carbons 1 and 3 on adjacent alpha-D-glucose rings.

“Alpha-D-glucose” herein can also be referred to as “glucose”.

The terms “poly alpha-1,3-glucan ether compound”, “poly alpha-1,3-glucanether”, “poly alpha-1,3-glucan ether derivative” and the like are usedinterchangeably herein. A poly alpha-1,3-glucan ether compound hereincan be represented by the structure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be a hydrogen atom (H) or an organic group. A polyalpha-1,3-glucan ether compound herein has a degree of substitution ofabout 0.05 to about 3.0. Poly alpha-1,3-glucan ether compounds disclosedin U.S. Appl. Publ. No. 2014/0179913 (incorporated herein by reference),and those disclosed herein, for example, can be used to prepare thecompositions of the present disclosure.

A poly alpha-1,3-glucan ether compound is termed an “ether” herein byvirtue of comprising the substructure —C_(G)—O—C—, where “—C_(G)—”represents carbon 2, 4, or 6 of a glucose monomeric unit of a polyalpha-1,3-glucan ether compound, and where “—C—” is comprised in theorganic group.

Poly alpha-1,3-glucan ether compounds disclosed herein are synthetic,man-made compounds.

An “organic group” group as used herein refers to a chain of one or morecarbons that (i) has the formula —C_(n)H_(2n+1) (i.e., an alkyl group,which is completely saturated) or (ii) is mostly saturated but has oneor more hydrogens substituted with another atom or functional group(i.e., a “substituted alkyl group”). Such substitution may be with oneor more hydroxyl groups, oxygen atoms (thereby forming an aldehyde orketone group), carboxyl groups, or other alkyl groups. In other words,where R is an organic group, R can be a chain of one or more saturatedcarbons, or a chain of carbons having one or more hydrogens substitutedwith a hydroxyl group, oxygen atom (thereby forming an aldehyde orketone group), carboxyl group, or alkyl group. An organic group hereinmay be uncharged or anionic (an example of an anionic organic group is acarboxy alkyl group).

A “hydroxy alkyl” group herein refers to a substituted alkyl group inwhich one or more hydrogen atoms of the alkyl group are substituted witha hydroxyl group. A “carboxy alkyl” group herein refers to a substitutedalkyl group in which one or more hydrogen atoms of the alkyl group aresubstituted with a carboxyl group.

A “halide” herein refers to a compound comprising one or more halogenatoms (e.g., fluorine, chlorine, bromine, iodine). A halide herein canrefer to a compound comprising one or more halide groups such asfluoride, chloride, bromide, or iodide. A halide group may serve as areactive group of an etherification agent.

An “etherification reaction” herein refers to a reaction comprising atleast poly alpha-1,3-glucan and an etherification agent. Thesecomponents are typically dissolved and/or mixed in an aqueous alkalihydroxide. A reaction is placed under suitable conditions (e.g., time,temperature) for the etherification agent to etherify one or morehydroxyl groups of the glucose units of poly alpha-1,3-glucan with anorganic group, thereby yielding a poly alpha-1,3-glucan ether compound.

The term “alkaline conditions” herein refers to a solution or mixture pHof at least 11 or 12. Alkaline conditions can be prepared by any meansknown in the art, such as by dissolving an alkali hydroxide in asolution or mixture.

The terms “etherification agent” and “alkylation agent” are usedinterchangeably herein. An etherification agent herein refers to anagent that can be used to etherify one or more hydroxyl groups of one ormore glucose units of poly alpha-1,3-glucan with an organic group. Anetherification agent thus comprises an organic group.

The term “poly alpha-1,3-glucan slurry” herein refers to an aqueousmixture comprising the components of a glucosyltransferase enzymaticreaction such as poly alpha-1,3-glucan, sucrose, one or moreglucosyltransferase enzymes, glucose and fructose. This composition is aslurry since the poly alpha-1,3-glucan is not dissolved therein.

The term “poly alpha-1,3-glucan wet cake” herein refers to polyalpha-1,3-glucan that has been separated from a slurry and washed withwater or an aqueous solution. Poly alpha-1,3-glucan is not completelydried when preparing a wet cake.

The term “degree of substitution” (DoS) as used herein refers to theaverage number of hydroxyl groups substituted in each monomeric unit(glucose) of a poly alpha-1,3-glucan ether compound. Since there arethree hydroxyl groups in each monomeric unit in poly alpha-1,3-glucan,the degree of substitution in a poly alpha-1,3-glucan ether compoundherein can be no higher than 3.

The term “molar substitution” (M.S.) as used herein refers to the molesof an organic group per monomeric unit of a poly alpha-1,3-glucan ethercompound. Alternatively, M.S. can refer to the average moles ofetherification agent used to react with each monomeric unit in polyalpha-1,3-glucan (M.S. can thus describe the degree of derivatization ofan etherification agent). It is noted that the M.S. value for polyalpha-1,3-glucan may have no upper limit. For example, when an organicgroup containing a hydroxyl group (e.g., hydroxyethyl or hydroxypropyl)has been etherified to poly alpha-1,3-glucan, the hydroxyl group of theorganic group may undergo further reaction, thereby coupling more of theorganic group to the poly alpha-1,3-glucan.

The term “crosslink” herein refers to a chemical bond, atom, or group ofatoms that connects two adjacent atoms in one or more polymer molecules.It should be understood that, in a composition comprising crosslinkedpoly alpha-1,3-glucan ether, crosslinks can be between at least two polyalpha-1,3-glucan ether molecules (i.e., intermolecular crosslinks);there can also be intramolecular crosslinking. A “crosslinking agent” asused herein is an atom or compound that can create crosslinks.

An “aqueous composition” herein has a liquid component that comprises atleast about 10 wt % water, for example. Examples of aqueous compositionsinclude mixtures, solutions, dispersions (e.g., colloidal dispersions),suspensions and emulsions, for example. Aqueous compositions in certainembodiments comprise one or more poly alpha-1,3-glucan ether compoundsthat are (i) dissolved in the aqueous composition (i.e., in solution),or (ii) not dissolved in the aqueous composition (e.g., present as acolloidal dispersion).

As used herein, the term “colloidal dispersion” refers to aheterogeneous system having a dispersed phase and a dispersion medium,i.e., microscopically dispersed insoluble particles (e.g., some forms ofpoly alpha-1,3-glucan ether herein) are suspended throughout anothersubstance (e.g., an aqueous composition such as water or aqueoussolution). An example of a colloidal dispersion herein is ahydrocolloid. All, or a portion of, the particles of a colloidaldispersion such as a hydrocolloid can comprise certain polyalpha-1,3-glucan ether compounds of the present disclosure. The terms“dispersant” and “dispersion agent” are used interchangeably herein torefer to a material that promotes the formation and/or stabilization ofa dispersion.

The terms “hydrocolloid” and “hydrogel” are used interchangeably herein.A hydrocolloid refers to a colloid system in which water or an aqueoussolution is the dispersion medium.

The term “aqueous solution” herein refers to a solution in which thesolvent comprises water. An aqueous solution can serve as a dispersantin certain aspects herein.

The term “viscosity” as used herein refers to the measure of the extentto which a fluid or an aqueous composition resists a force tending tocause it to flow. Various units of viscosity that can be used hereininclude centipoise (cPs) and Pascal-second (Pa·s). One poise is equal to0.100 kg·m⁻¹·s⁻¹, or 1 mPa·s. Thus, the terms “viscosity modifier” and“viscosity-modifying agent” as used herein refer to anything that canalter/modify the viscosity of a fluid or aqueous composition.

The term “shear thinning behavior” as used herein refers to a decreasein the viscosity of the hydrocolloid or aqueous solution as shear rateincreases. The term “shear thickening behavior” as used herein refers toan increase in the viscosity of the hydrocolloid or aqueous solution asshear rate increases. “Shear rate” herein refers to the rate at which aprogressive shearing deformation is applied to the hydrocolloid oraqueous solution. A shearing deformation can be applied rotationally.

The term “contacting” as used herein, such as with contacting polyalpha-1,3-glucan, a poly alpha-1,3-glucan ether compound, and/orcellulase with an aqueous composition, can be performed by any meansknown in the art, such as dissolving, mixing, shaking, orhomogenization, for example.

The “molecular weight” of poly alpha-1,3-glucan and polyalpha-1,3-glucan ether compounds herein can be represented asnumber-average molecular weight (M_(n)) or as weight-average molecularweight (M_(w)). Alternatively, molecular weight can be represented asDaltons, grams/mole, DPw (weight average degree of polymerization), orDPn (number average degree of polymerization). Various means are knownin the art for calculating these molecular weight measurements, such ashigh-pressure liquid chromatography (HPLC), size exclusionchromatography (SEC), or gel permeation chromatography (GPC).

The terms “percent by volume”, “volume percent”, “vol %”, “v/v %” andthe like are used interchangeably herein. The percent by volume of asolute in a solution can be determined using the formula: [(volume ofsolute)/(volume of solution)]×100%.

The terms “percent by weight”, “weight percentage (wt %)”,“weight-weight percentage (% w/w)” and the like are used interchangeablyherein. Percent by weight refers to the percentage of a material on amass basis as it is comprised in a composition, mixture or solution.

The term “increased” as used herein can refer to a quantity or activitythat is at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%,12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 50%, 100%, or 200% morethan the quantity or activity for which the increased quantity oractivity is being compared. The terms “increased”, “elevated”,“enhanced”, “greater than”, “improved” and the like are usedinterchangeably herein.

Development of new polysaccharide polymers that provide the benefits ofcellulosic polymers, but that are resistant to cellulase, is desirable.Poly alpha-1,3-glucan ether compounds are disclosed herein as a superioralternative to cellulosic polymers, since they are stable (resistant) tocellulase and have other features useful in formulations such asdetergents.

Embodiments of the present disclosure concern a composition comprising acellulase and a poly alpha-1,3-glucan ether compound represented by thestructure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be an H or an organic group. Furthermore, the polyalpha-1,3-glucan ether compound has a degree of substitution with theorganic group of about 0.05 to about 3.0.

Significantly, a poly alpha-1,3-glucan ether compound of the disclosurecan modify the viscosity and rheological properties of an aqueoussolution to which it is added, and also adsorb to surfaces such as afabric surface. Furthermore, since poly alpha-1,3-glucan ether compoundsherein are stable to cellulase activity, one or more cellulase enzymescan be included in a composition comprising the glucan ether compound.Thus, a composition herein can optionally be characterized as one forwhich including a cellulase is beneficial to the utility of thecomposition.

One or more cellulase enzymes are comprised in the disclosedcomposition. A cellulase herein can have endocellulase activity (EC3.2.1.4), exocellulase activity (EC 3.2.1.91), or cellobiase activity(EC 3.2.1.21). A cellulase herein is an “active cellulase” havingactivity under suitable conditions for maintaining cellulase activity;it is within the skill of the art to determine such suitable conditions.Besides being able to degrade cellulose, a cellulase in certainembodiments can also degrade cellulose ether derivatives such ascarboxymethyl cellulose. Examples of cellulose ether derivatives whichare expected to not be stable to cellulase are disclosed in U.S. Pat.Nos. 7,012,053, 7,056,880, 6,579,840, 7,534,759 and 7,576,048.

A cellulase herein may be derived from any microbial source, such as abacteria or fungus. Chemically-modified cellulases or protein-engineeredmutant cellulases are included. Suitable cellulases include, but are notlimited to, cellulases from the genera Bacillus, Pseudomonas,Streptomyces, Trichoderma, Humicola, Fusarium, Thielavia and Acremonium.As other examples, a cellulase may be derived from Humicola insolens,Myceliophthora thermophila or Fusarium oxysporum; these and othercellulases are disclosed in U.S. Pat. Nos. 4,435,307, 5,648,263,5,691,178, 5,776,757 and 7,604,974, which are all incorporated herein byreference. Exemplary Trichoderma reesei cellulases are disclosed in U.S.Pat. Nos. 4,689,297, 5,814,501, 5,324,649, and International PatentAppl. Publ. Nos. WO92/06221 and WO92/06165, all of which areincorporated herein by reference. Exemplary Bacillus cellulases aredisclosed in U.S. Pat. No. 6,562,612, which is incorporated herein byreference. A cellulase, such as any of the foregoing, preferably is in amature form lacking an N-terminal signal peptide. Commercially availablecellulases useful herein include CELLUZYME® and CAREZYME® (NovozymesA/S); CLAZINASE® and PURADAX® HA (DuPont Industrial Biosciences), andKAC-500(B)®(Kao Corporation).

Alternatively, a cellulase herein may be produced by any means known inthe art, such as described in U.S. Pat. Nos. 4,435,307, 5,776,757 and7,604,974, which are incorporated herein by reference. For example, acellulase may be produced recombinantly in a heterologous expressionsystem, such as a microbial or fungal heterologous expression system.Examples of heterologous expression systems include bacterial (e.g., E.coli, Bacillus sp.) and eukaryotic systems. Eukaryotic systems canemploy yeast (e.g., Pichia sp., Saccharomyces sp.) or fungal (e.g.,Trichoderma sp. such as T. reesei, Aspergillus species such as A. niger)expression systems, for example.

One or more cellulases can be directly added as an ingredient whenpreparing the disclosed composition. Alternatively, one or morecellulases can be indirectly (inadvertently) provided in the disclosedcomposition. For example, cellulase can be provided in a compositionherein by virtue of being present in a non-cellulase enzyme preparationused for preparing the composition. Cellulase in compositions in whichcellulase is indirectly provided thereto can be present at about 0.1-10ppb (e.g., less than 1 ppm), for example. A benefit of a compositionherein, by virtue of employing a poly alpha-1,3-glucan ether compoundinstead of a cellulose ether compound, is that non-cellulase enzymepreparations that might have background cellulase activity can be usedwithout concern that the desired effects of the glucan ether will benegated by the background cellulase activity.

A cellulase in certain embodiments can be thermostable. Cellulasethermostability refers to the ability of the enzyme to retain activityafter exposure to an elevated temperature (e.g. about 60-70° C.) for aperiod of time (e.g., about 30-60 minutes). The thermostability of acellulase can be measured by its half-life (t½) given in minutes, hours,or days, during which time period half the cellulase activity is lostunder defined conditions.

A cellulase in certain embodiments can be stable to a wide range of pHvalues (e.g. neutral or alkaline pH such as pH of ˜7.0 to ˜11.0). Suchenzymes can remain stable for a predetermined period of time (e.g., atleast about 15 min., 30 min., or 1 hour) under such pH conditions.

At least one, two, or more cellulases may be included in thecomposition. The total amount of cellulase in a composition hereintypically is an amount that is suitable for the purpose of usingcellulase in the composition (an “effective amount”). For example, aneffective amount of cellulase in a composition intended for improvingthe feel and/or appearance of a cellulose-containing fabric is an amountthat produces measurable improvements in the feel of the fabric (e.g.,improving fabric smoothness and/or appearance, removing pills andfibrils which tend to reduce fabric appearance sharpness). As anotherexample, an effective amount of cellulase in a fabric stonewashingcomposition herein is that amount which will provide the desired effect(e.g., to produce a worn and faded look in seams and on fabric panels).The amount of cellulase in a composition herein can also depend on theprocess parameters in which the composition is employed (e.g.,equipment, temperature, time, and the like) and cellulase activity, forexample. The effective concentration of cellulase in an aqueouscomposition in which a fabric is treated can be readily determined by askilled artisan. In fabric care processes, cellulase can be present inan aqueous composition (e.g., wash liquor) in which a fabric is treatedin a concentration that is minimally about 0.01-0.1 ppm total cellulaseprotein, or about 0.1-10 ppb total cellulase protein (e.g., less than 1ppm), to maximally about 100, 200, 500, 1000, 2000, 3000, 4000, or 5000ppm total cellulase protein, for example.

Poly alpha-1,3 glucan and/or poly alpha-1,3-glucan ethers herein aremostly or completely stable (resistant) to being degraded by cellulase.For example, the percent degradation of a poly alpha-1,3 glucan and/orpoly alpha-1,3-glucan ether compound by one or more cellulases is lessthan 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1%, or is 0%. Such percentdegradation can be determined, for example, by comparing the molecularweight of polymer before and after treatment with a cellulase for aperiod of time (e.g., ˜24 hours).

The degree of substitution (DoS) of a poly alpha-1,3-glucan ethercompound in a composition disclosed herein is about 0.5 to about 3.0.Alternatively, the DoS can be about 0.2 to about 2.0. Alternativelystill, the DoS can be at least about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2,2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. It would be understood bythose skilled in the art that since a poly alpha-1,3-glucan ethercompound herein has a degree of substitution between about 0.05 to about3.0, and by virtue of being an ether, the R groups of the compoundcannot only be hydrogen.

The DoS of a poly alpha-1,3-glucan ether compound herein can affect theviscosity of an aqueous composition in which it may be comprised. Forexample, an aqueous composition herein comprising carboxymethyl polyalpha-1,3-glucan (CMG) with a DoS of about 0.4-0.6 is believed to have agreater viscosity than an aqueous composition comprising CMG with higherDoS (e.g., about 0.8-1.0).

The percentage of glycosidic linkages between the glucose monomericunits of poly alpha-1,3-glucan ether compounds herein that are alpha-1,3is at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or100% (or any integer between 50% and 100%. In such embodiments,accordingly, the compound has less than about 50%, 40%, 30%, 20%, 10%,5%, 4%, 3%, 2%, 1%, or 0% (or any integer value between 0% and 50%) ofglycosidic linkages that are not alpha-1,3.

The backbone of a poly alpha-1,3-glucan ether compound herein ispreferably linear/unbranched. In certain embodiments, the compound hasno branch points or less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%,or 1% branch points as a percent of the glycosidic linkages in thepolymer. Examples of branch points include alpha-1,6 branch points.

The formula of a poly alpha-1,3-glucan ether compound comprised in acomposition herein has an n value of at least 6. Alternatively, n canhave a value of at least 25, 50, 75, 100, 150, 200, 250, 300, 350, 400,450, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600,1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800,2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, or4000 (or any integer between 25 and 4000), for example. The value of nin still other examples can be in a range of 25-250, 50-250, 75-250,100-250, 150-250, 200-250, 25-200, 50-200, 75-200, 100-200, 150-200,25-150, 50-150, 75-150, 100-150, 25-100, 50-100, 75-100, 25-75, 50-75,or 25-50.

The molecular weight of a poly alpha-1,3-glucan ether compound hereincan be measured as number-average molecular weight (M_(n)) or asweight-average molecular weight (M_(w)). Alternatively, molecular weightcan be measured in Daltons or grams/mole. It may also be useful to referto the DP_(w) (weight average degree of polymerization) or DP_(n)(number average degree of polymerization) of the poly alpha-1,3-glucanpolymer component of the compound.

The M_(n) or M_(w) of poly alpha-1,3-glucan ether compounds herein maybe at least about 1000. Alternatively, the M_(n) or M_(w) can be atleast about 1000 to about 600000. Alternatively still, the M_(n) orM_(w) can be at least about 2000, 3000, 4000, 5000, 6000, 7000, 8000,9000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000,75000, 100000, 150000, 200000, 250000, 300000, 350000, 400000, 450000,500000, 550000, or 600000 (or any integer between 2000 and 600000), forexample.

Each R group in the formula of a poly alpha-1,3-glucan ether compoundherein can independently be an H or an organic group. An organic groupmay be an alkyl group such as a methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, or decyl group, for example.

Alternatively, an organic group may be a substituted alkyl group inwhich there is a substitution on one or more carbons of the alkyl group.The substitution(s) may be one or more hydroxyl, aldehyde, ketone,and/or carboxyl groups. For example, a substituted alkyl group may be ahydroxy alkyl group, dihydroxy alkyl group, or carboxy alkyl group.

Examples of suitable hydroxy alkyl groups are hydroxymethyl (—CH₂OH),hydroxyethyl (e.g., —CH₂CH₂OH, —CH(OH)CH₃), hydroxypropyl (e.g.,—CH₂CH₂CH₂OH, —CH₂CH(OH)CH₃, —CH(OH)CH₂CH₃), hydroxybutyl andhydroxypentyl groups. Other examples include dihydroxy alkyl groups(diols) such as dihydroxymethyl, dihydroxyethyl (e.g., —CH(OH)CH₂OH),dihydroxypropyl (e.g., —CH₂CH(OH)CH₂OH, —CH(OH)CH(OH)CH₃),dihydroxybutyl and dihydroxypentyl groups.

Examples of suitable carboxy alkyl groups are carboxymethyl (—CH₂COOH),carboxyethyl (e.g., —CH₂CH₂COOH, —CH(COOH)CH₃), carboxypropyl (e.g.,—CH₂CH₂CH₂COOH, —CH₂CH(COOH)CH₃, —CH(COOH)CH₂CH₃), carboxybutyl andcarboxypentyl groups.

Alternatively still, one or more carbons of an alkyl group can have asubstitution(s) with another alkyl group. Examples of such substituentalkyl groups are methyl, ethyl and propyl groups. To illustrate, an Rgroup can be —CH(CH₃)CH₂CH₃ or —CH₂CH(CH₃)CH₃, for example, which areboth propyl groups having a methyl substitution.

As should be clear from the above examples of various substituted alkylgroups, a substitution (e.g., hydroxy or carboxy group) on an alkylgroup in certain embodiments may be bonded to the terminal carbon atomof the alkyl group, where the terminal carbon group is opposite theterminus that is in ether linkage to the glucose group in the glucanether compound (above formula). An example of this terminal substitutionis in the hydroxypropyl group —CH₂CH₂CH₂OH. Alternatively, asubstitution may be on an internal carbon atom of an alkyl group. Anexample on an internal substitution is in the hydroxypropyl group—CH₂CH(OH)CH₃. An alkyl group can have one or more substitutions, whichmay be the same (e.g., two hydroxyl groups [dihydroxy]) or different(e.g., a hydroxyl group and a carboxyl group).

Poly alpha-1,3-glucan ether compounds in certain embodiments disclosedherein may contain one type of organic group. For example, one or more Rgroups ether-linked to the glucose group in the above formula may be amethyl group; the R groups in this particular example would thusindependently be hydrogen and methyl groups. Such a compound can bereferred to as ethyl poly alpha-1,3-glucan. As another example, one ormore R groups ether-linked to the glucose group in the above formula maybe a carboxymethyl group; the R groups in this particular example wouldthus independently be hydrogen and carboxymethyl groups. Such a compoundcan be referred to as carboxymethyl poly alpha-1,3-glucan (CMG).

Alternatively, poly alpha-1,3-glucan ether compounds comprised in acomposition herein can contain two or more different types of organicgroups. Examples of such compounds contain (i) two different alkylgroups as R groups, (ii) an alkyl group and a hydroxy alkyl group as Rgroups (alkyl hydroxyalkyl poly alpha-1,3-glucan, generically speaking),(iii) an alkyl group and a carboxy alkyl group as R groups (alkylcarboxyalkyl poly alpha-1,3-glucan, generically speaking), (iv) ahydroxy alkyl group and a carboxy alkyl group as R groups (hydroxyalkylcarboxyalkyl poly alpha-1,3-glucan, generically speaking), (v) twodifferent hydroxy alkyl groups as R groups, or (vi) two differentcarboxy alkyl groups as R groups. Specific non-limiting examples of suchcompounds include ethyl hydroxyethyl poly alpha-1,3-glucan (i.e., whereR groups are independently H, ethyl, or hydroxyethyl), hydroxyalkylmethyl poly alpha-1,3-glucan (i.e., where R groups are independently H,hydroxyalkyl, or methyl), carboxymethyl hydroxyethyl polyalpha-1,3-glucan (i.e., where R groups are independently H,carboxymethyl, or hydroxyethyl), and carboxymethyl hydroxypropyl polyalpha-1,3-glucan (i.e., where R groups are independently H,carboxymethyl, or hydroxypropyl).

Poly alpha-1,3-glucan ether compounds herein can comprise at least onenonionic organic group and at least one anionic group, for example. Asanother example, poly alpha-1,3-glucan ether compounds herein cancomprise at least one nonionic organic group and at least one positivelycharged organic group.

A composition comprising (i) cellulase and (ii) poly alpha-1,3-glucanand/or a poly alpha-1,3-glucan ether compound in certain embodiments canbe non-aqueous (e.g., a dry composition). Examples of such embodimentsinclude powders, granules, microcapsules, flakes, or any other form ofparticulate matter. Other examples include larger compositions such aspellets, bars, kernels, beads, tablets, sticks, or other agglomerates. Anon-aqueous or dry composition herein typically has less than 3, 2, 1,0.5, or 0.1 wt % water comprised therein. A non-aqueous compositionherein can comprise about 0.0001 wt % to about 2.0 wt % one or morecellulases, for example. Methods for preparing dry compositionscomprising active enzymes such as cellulases are well known in the art.

A composition comprising a cellulase and a poly alpha-1,3-glucan ethercompound in certain embodiments is an aqueous composition. An aqueouscomposition herein is a solution or mixture in which the solvent is atleast about 10 wt % water. In other embodiments, the solvent in anaqueous composition is at least about 20, 30, 40, 50, 60, 70, 80, 90, or100 wt % water (or any integer value between 10 and 100 wt %). Examplesof aqueous compositions herein are aqueous solutions, mixtures andhydrocolloids.

An aqueous composition comprising a cellulase and a polyalpha-1,3-glucan ether compound has a viscosity of at least about 10 cPsin certain embodiments. Alternatively, an aqueous composition herein hasa viscosity of at least about 100, 250, 500, 750, 1000, 1500, 2000,2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000,8500, 9000, 9500, 10000, 10500, 11000, 12000, 13000, 14000, 15000,20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, or 100000 cPs(or any integer between 100 and 100000 cPs), for example.

Viscosity can be measured for an aqueous composition herein at anytemperature between about 3° C. to about 110° C. (or any integer between3 and 110° C.), for example. Alternatively, viscosity can be measured ata temperature between about 4° C. to 30° C., or about 20° C. to 25° C.Viscosity can be measured at atmospheric pressure (about 760 torr) orany other higher or lower pressure.

The viscosity of an aqueous composition disclosed herein can be measuredusing a viscometer or rheometer, or using any other means known in theart. It would be understood by those skilled in the art that a rheometercan be used to measure the viscosity of those aqueous compositions ofthe disclosure that exhibit shear thinning behavior or shear thickeningbehavior (i.e., liquids with viscosities that vary with flowconditions). The viscosity of such embodiments can be measured at arotational shear rate of about 10 to 1000 rpm (revolutions per minute)(or any integer between 10 and 1000 rpm), for example. Alternatively,viscosity can be measured at a rotational shear rate of about 10, 60,150, 250, or 600 rpm.

The pH of an aqueous composition disclosed herein can be between about2.0 to about 12.0. Alternatively, pH can be about 2.0, 3.0, 4.0, 5.0,6.0, 7.0, 8.0, 9.0, 10.0, 11.0, 12.0; or between 5.0 to about 12.0; orbetween about 4.0 to about 8.0; or between about 3.0 and 11.0. A skilledartisan would be able to select and provide a pH or pH range that issuitable for maintaining cellulase activity in an aqueous compositionherein. In certain embodiments, the viscosity of the disclosed aqueouscomposition does not largely fluctuate at a pH between about 3.0 and11.0.

A poly alpha-1,3-glucan ether compound can be present in a compositionherein, such as an aqueous composition, at a wt % of about, or at leastabout, 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0,1.2, 1.4, 1.6, 1.8, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5, 6, 7, 8, 9, 10, 11,12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29,30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,48, 49, 50, 51, 52, 53, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66,67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84,85, 86, 87, 88, 89, or 90 wt %, for example.

Compositions in certain embodiments herein may comprise a celluloseether compound (e.g., carboxymethyl cellulose [CMC]), whereas there isno cellulose ether compound (e.g., CMC) in other embodiments. It ispreferable that a cellulose ether compound is absent, as it would besubject to degradation by one or more cellulase enzymes present in thedisclosed composition.

A composition herein, such as an aqueous composition, can comprise othercomponents in addition to cellulase and one or more polyalpha-1,3-glucan ether compounds. For example, the composition cancomprise one or more salts such as a sodium salts (e.g., NaCl, Na₂SO₄).Other non-limiting examples of salts include those having (i) analuminum, ammonium, barium, calcium, chromium (II or III), copper (I orII), iron (II or III), hydrogen, lead (II), lithium, magnesium,manganese (II or III), mercury (I or II), potassium, silver, sodiumstrontium, tin (II or IV), or zinc cation, and (ii) an acetate, borate,bromate, bromide, carbonate, chlorate, chloride, chlorite, chromate,cyanamide, cyanide, dichromate, dihydrogen phosphate, ferricyanide,ferrocyanide, fluoride, hydrogen carbonate, hydrogen phosphate, hydrogensulfate, hydrogen sulfide, hydrogen sulfite, hydride, hydroxide,hypochlorite, iodate, iodide, nitrate, nitride, nitrite, oxalate, oxide,perchlorate, permanganate, peroxide, phosphate, phosphide, phosphite,silicate, stannate, stannite, sulfate, sulfide, sulfite, tartrate, orthiocyanate anion. Thus, any salt having a cation from (i) above and ananion from (ii) above can be in a composition comprising cellulase and apoly alpha-1,3-glucan ether compound, for example. A salt can be presentin a composition herein at a wt % of about 0.01% to about 10.00% (or anyhundredth increment between 0.01% and 10.00%), for example. One skilledin the art would be able to determine those salts that can be used incombination with a cellulase such that it maintains enzymatic activity.

Those skilled in the art would understand that in certain embodiments ofthe present disclosure, a poly alpha-1,3-glucan ether compound can be inan anionic form when provided in an aqueous composition. Examples mayinclude those poly alpha-1,3-glucan ether compounds having an organicgroup comprising an alkyl group substituted with a carboxyl group.Carboxyl (COOH) groups in a carboxyalkyl poly alpha-1,3-glucan ethercompound can convert to carboxylate (COO⁻) groups in aqueous conditions.Such anionic groups can interact with salt cations such as any of thoselisted above in (i) (e.g., potassium, sodium, or lithium cation). Thus,a poly alpha-1,3-glucan ether compound can be a sodium carboxyalkyl polyalpha-1,3-glucan ether (e.g., sodium carboxymethyl polyalpha-1,3-glucan), potassium carboxyalkyl poly alpha-1,3-glucan ether(e.g., potassium carboxymethyl poly alpha-1,3-glucan), or lithiumcarboxyalkyl poly alpha-1,3-glucan ether (e.g., lithium carboxymethylpoly alpha-1,3-glucan), for example.

A poly alpha-1,3-glucan ether compound comprised in certain embodimentsof the disclosed composition may be crosslinked using any means known inthe art. Such crosslinks may be borate crosslinks, where the borate isfrom any boron-containing compound (e.g., boric acid, diborates,tetraborates, pentaborates, polymeric compounds such as Polybor®,polymeric compounds of boric acid, alkali borates), for example.Alternatively, crosslinks can be provided with polyvalent metals such astitanium or zirconium, for example. Titanium crosslinks may be provided,for example, using titanium IV-containing compounds such as titaniumammonium lactate, titanium triethanolamine, titanium acetylacetonate,and polyhydroxy complexes of titanium. Zirconium crosslinks can beprovided using zirconium IV-containing compounds such as zirconiumlactate, zirconium carbonate, zirconium acetylacetonate, zirconiumtriethanolamine, zirconium diisopropylamine lactate and polyhydroxycomplexes of zirconium, for example. Alternatively still, crosslinks canbe provided with any crosslinking agent described in U.S. Pat. Nos.4,462,917, 4,464,270, 4,477,360 and 4,799,550, which are allincorporated herein by reference. A crosslinking agent (e.g., borate)may be present in a composition herein at a wt % of about 0.2 to 20 wt%, or about 0.1, 0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15,or 20 wt %, for example.

A poly alpha-1,3-glucan ether compound disclosed herein that iscrosslinked typically has a higher viscosity in an aqueous compositioncompared to its non-crosslinked counterpart. In addition, a crosslinkedpoly alpha-1,3-glucan ether compound can have increased shear thickeningbehavior compared to its non-crosslinked counterpart. For example, aborate-crosslinked hydroxyalkyl poly alpha-1,3-glucan ether compound(e.g., dihydroxypropyl glucan ether) can have increased shear thickeningbehavior compared to its non-crosslinked counterpart.

A composition herein may contain one or more different active enzymes inaddition to at least one cellulase. Non-limiting examples of such otherenzymes include proteases, hemicellulases, peroxidases, lipolyticenzymes (e.g., metallolipolytic enzymes), xylanases, lipases,phospholipases, esterases (e.g., arylesterase, polyesterase),perhydrolases, cutinases, pectinases, pectate lyases, mannanases,keratinases, reductases, oxidases (e.g., choline oxidase),phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, beta-glucanases, arabinosidases,hyaluronidases, chondroitinases, laccases, metalloproteinases,amadoriases, glucoamylases, arabinofuranosidases, phytases, isomerases,transferases and amylases. Cellulase and optionally one or moreadditional enzymes may each be comprised in a composition herein atabout 0.0001-0.1 wt % (e.g., 0.01-0.03 wt %) active enzyme (e.g.,calculated as pure enzyme protein), for example.

The Examples disclosed herein demonstrate that aqueous compositionscomprising a poly alpha-1,3-glucan ether compound herein can have shearthinning behavior or shear thickening behavior. It is expected that suchaqueous compositions, which additionally comprise one or morecellulases, also have these rheological properties. Shear thinningbehavior is observed as a decrease in viscosity of the aqueouscomposition as shear rate increases, whereas shear thickening behavioris observed as an increase in viscosity of the aqueous composition asshear rate increases. Modification of the shear thinning behavior orshear thickening behavior of an aqueous solution herein is due to theadmixture of a poly alpha-1,3-glucan ether composition to the aqueouscomposition. Thus, one or more poly alpha-1,3-glucan ether compounds ofthe disclosure can be added to an aqueous composition to modify itsrheological profile (i.e., the flow properties of the aqueouscomposition are modified). Also, one or more poly alpha-1,3-glucan ethercompounds can be added to an aqueous composition to modify itsviscosity.

The rheological properties of aqueous compositions herein can beobserved by measuring viscosity over an increasing rotational shear rate(e.g., from about 10 rpm to about 250 rpm). For example, shear thinningbehavior of an aqueous composition disclosed herein can be observed as adecrease in viscosity (cPs) by at least about 5%, 10%, 15%, 20%, 25%,30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%(or any integer between 5% and 95%) as the rotational shear rateincreases from about 10 rpm to 60 rpm, 10 rpm to 150 rpm, 10 rpm to 250rpm, 60 rpm to 150 rpm, 60 rpm to 250 rpm, or 150 rpm to 250 rpm. Asanother example, shear thickening behavior of an aqueous compositiondisclosed herein can be observed as an increase in viscosity (cPs) by atleast about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%,65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 125%, 150%, 175%, or 200% (orany integer between 5% and 200%) as the rotational shear rate increasesfrom about 10 rpm to 60 rpm, 10 rpm to 150 rpm, 10 rpm to 250 rpm, 60rpm to 150 rpm, 60 rpm to 250 rpm, or 150 rpm to 250 rpm.

A composition disclosed herein, such as an aqueous composition, can bein the form of a personal care product, pharmaceutical product,household product, or industrial product in which having one or morecellulase enzymes optionally increases the effectiveness of the product.Poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compoundsherein can be used as thickening agents and/or dispersion agents in eachof these products, if desired, when in an aqueous form. Such athickening agent may optionally be used in conjunction with one or moreother types of thickening agents, such as those disclosed in U.S. Pat.No. 8,541,041, the disclosure of which is incorporated herein byreference.

Personal care products herein are not particularly limited and include,for example, skin care compositions, cosmetic compositions, antifungalcompositions, and antibacterial compositions. Personal care productsherein may be in the form of, for example, lotions, creams, pastes,balms, ointments, pomades, gels, liquids, combinations of these and thelike. The personal care products disclosed herein can include at leastone active ingredient, if desired. An active ingredient is generallyrecognized as an ingredient that causes an intended pharmacologicaleffect.

In certain embodiments, a skin care product can include at least oneactive ingredient for the treatment or prevention of skin ailments,providing a cosmetic effect, or for providing a moisturizing benefit toskin, such as zinc oxide, petrolatum, white petrolatum, mineral oil, codliver oil, lanolin, dimethicone, hard fat, vitamin A, allantoin,calamine, kaolin, glycerin, or colloidal oatmeal, and combinations ofthese. A skin care product may include one or more natural moisturizingfactors such as ceramides, hyaluronic acid, glycerin, squalane, aminoacids, cholesterol, fatty acids, triglycerides, phospholipids,glycosphingolipids, urea, linoleic acid, glycosaminoglycans,mucopolysaccharide, sodium lactate, or sodium pyrrolidone carboxylate,for example. Other ingredients that may be included in a skin careproduct include, without limitation, glycerides, apricot kernel oil,canola oil, squalane, squalene, coconut oil, corn oil, jojoba oil,jojoba wax, lecithin, olive oil, safflower oil, sesame oil, shea butter,soybean oil, sweet almond oil, sunflower oil, tea tree oil, shea butter,palm oil, cholesterol, cholesterol esters, wax esters, fatty acids, andorange oil.

A personal care product herein can also be in the form of makeup,lipstick, mascara, rouge, foundation, blush, eyeliner, lip liner, lipgloss, other cosmetics, sunscreen, sun block, nail polish, mousse, hairspray, styling gel, nail conditioner, bath gel, shower gel, body wash,face wash, shampoo, hair conditioner (leave-in or rinse-out), creamrinse, hair dye, hair coloring product, hair shine product, hair serum,hair anti-frizz product, hair split-end repair product, lip balm, skinconditioner, cold cream, moisturizer, body spray, soap, body scrub,exfoliant, astringent, scruffing lotion, depilatory, permanent wavingsolution, antidandruff formulation, antiperspirant composition,deodorant, shaving product, pre-shaving product, after-shaving product,cleanser, skin gel, rinse, dentifrice composition, toothpaste, ormouthwash, for example.

A pharmaceutical product herein can be in the form of an emulsion,liquid, elixir, gel, suspension, solution, cream, or ointment, forexample. Also, a pharmaceutical product herein can be in the form of anyof the personal care products disclosed herein, such as an antibacterialor antifungal composition. A pharmaceutical product can further compriseone or more pharmaceutically acceptable carriers, diluents, and/orpharmaceutically acceptable salts. A poly alpha-1,3-glucan ethercompound disclosed herein can also be used in capsules, encapsulants,tablet coatings, and as an excipients for medicaments and drugs.

A household and/or industrial product herein can be in the form ofdrywall tape-joint compounds; mortars; grouts; cement plasters; sprayplasters; cement stucco; adhesives; pastes; wall/ceiling texturizers;binders and processing aids for tape casting, extrusion forming,injection molding and ceramics; spray adherents andsuspending/dispersing aids for pesticides, herbicides, and fertilizers;fabric care products such as fabric softeners and laundry detergents;hard surface cleaners; air fresheners; polymer emulsions; gels such aswater-based gels; surfactant solutions; paints such as water-basedpaints; protective coatings; adhesives; sealants and caulks; inks suchas water-based ink; hydraulic fluids (e.g., those used for fracking indownhole operations); and aqueous mineral slurries, for example.

Poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compounddisclosed herein can be comprised in a personal care product,pharmaceutical product, household product, or industrial product in anamount that provides a desired degree of thickening or dispersion, forexample. Examples of a concentration or amount of a polyalpha-1,3-glucan ether compound in a product, on a weight basis, can beabout 0.1-3 wt %, 1-2 wt %, 1.5-2.5 wt %, 2.0 wt %, 0.1-4 wt %, 0.1-5 wt%, or 0.1-10 wt %.

Compositions disclosed herein can be in the form of a fabric carecomposition. A fabric care composition herein can be used for hand wash,machine wash and/or other purposes such as soaking and/or pretreatmentof fabrics, for example. A fabric care composition may take the form of,for example, a laundry detergent; fabric conditioner; any wash-, rinse-,or dryer-added product; unit dose; or spray. Fabric care compositions ina liquid form may be in the form of an aqueous composition as disclosedherein. In other aspects, a fabric care composition can be in a dry formsuch as a granular detergent or dryer-added fabric softener sheet. Othernon-limiting examples of fabric care compositions herein include:granular or powder-form all-purpose or heavy-duty washing agents;liquid, gel or paste-form all-purpose or heavy-duty washing agents;liquid or dry fine-fabric (e.g., delicates) detergents; cleaningauxiliaries such as bleach additives, “stain-stick”, or pre-treatments;substrate-laden products such as dry and wetted wipes, pads, or sponges;sprays and mists.

A cellulase can be incorporated into a detergent at or near aconcentration conventionally used for cellulase in detergents. Forexample, a cellulase may be added in an amount corresponding to about0.00001-1 mg, or about 0.01-100 mg, of cellulase (calculated as pureenzyme protein) per liter of wash liquor or dishwasher liquor. Exemplaryformulations are provided herein.

A cellulase may be a component of a detergent composition, as the onlyenzyme or with other enzymes including other cellulase enzymes. As such,it may be included in a detergent composition in the form of anon-dusting granulate, a stabilized liquid, or a protected enzyme, forexample. Non-dusting granulates may be produced, e.g., as disclosed inU.S. Pat. Nos. 4,106,991 and 4,661,452 (which are incorporated herein byreference) and may optionally be coated by methods known in the art.Examples of waxy coating materials are poly(ethylene oxide) products(e.g., polyethylene glycol, PEG) with mean molar weights of 1000 to20000; ethoxylated nonylphenols having from 16 to 50 ethylene oxideunits; ethoxylated fatty alcohols in which the alcohol contains from 12to 20 carbon atoms and in which there are 15 to 80 ethylene oxide units;fatty alcohols; fatty acids; and mono- and di- and triglycerides offatty acids. Examples of coating materials suitable for application byfluid bed techniques are given in, for example, GB 1483591, which isincorporated herein by reference. Liquid enzyme preparations may, forinstance, be stabilized by adding a polyol such as propylene glycol, asugar or sugar alcohol, lactic acid or boric acid according toestablished methods. Other enzyme stabilizers known in the art can beused. Protected enzymes may be prepared according to the methoddisclosed in, for example, EP238216, which is incorporated herein byreference.

A detergent composition herein may be in any useful form, e.g., aspowders, granules, pastes, bars, unit dose or liquid. A liquid detergentmay be aqueous, typically containing up to about 70 wt % of water and 0wt % to about 30 wt % of organic solvent. It may also be in the form ofa compact gel type containing only about 30 wt % water.

A detergent composition herein typically comprises one or moresurfactants, wherein the surfactant is selected from nonionicsurfactants, anionic surfactants, cationic surfactants, ampholyticsurfactants, zwitterionic surfactants, semi-polar nonionic surfactantsand mixtures thereof. In some embodiments, the surfactant is present ata level of from about 0.1% to about 60%, while in alternativeembodiments the level is from about 1% to about 50%, while in stillfurther embodiments the level is from about 5% to about 40%, by weightof the detergent composition. A detergent will usually contain 0 wt % toabout 50 wt % of an anionic surfactant such as linearalkylbenzenesulfonate (LAS), alpha-olefinsulfonate (AOS), alkyl sulfate(fatty alcohol sulfate) (AS), alcohol ethoxysulfate (AEOS or AES),secondary alkanesulfonates (SAS), alpha-sulfo fatty acid methyl esters,alkyl- or alkenylsuccinic acid, or soap. In addition, a detergentcomposition may optionally contain 0 wt % to about 40 wt % of a nonionicsurfactant such as alcohol ethoxylate (AEO or AE), carboxylated alcoholethoxylates, nonylphenol ethoxylate, alkylpolyglycoside,alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fattyacid monoethanolamide, or polyhydroxy alkyl fatty acid amide (asdescribed for example in WO92/06154, which is incorporated herein byreference).

A detergent composition herein typically comprises one or more detergentbuilders or builder systems. In some embodiments incorporating at leastone builder, the cleaning compositions comprise at least about 1%, fromabout 3% to about 60%, or even from about 5% to about 40%, builder byweight of the composition. Builders include, but are not limited to,alkali metal, ammonium and alkanolammonium salts of polyphosphates,alkali metal silicates, alkaline earth and alkali metal carbonates,aluminosilicates, polycarboxylate compounds, etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonicacid, and carboxymethyloxysuccinic acid, various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, citric acid,oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof. Indeed, it iscontemplated that any suitable builder will find use in variousembodiments of the present disclosure. Examples of a detergent builderor complexing agent include zeolite, diphosphate, triphosphate,phosphonate, citrate, nitrilotriacetic acid (NTA),ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaaceticacid (DTMPA), alkyl- or alkenylsuccinic acid, soluble silicates orlayered silicates (e.g., SKS-6 from Hoechst). A detergent may also beunbuilt, i.e., essentially free of detergent builder.

In some embodiments, builders form water-soluble hardness ion complexes(e.g., sequestering builders), such as citrates and polyphosphates(e.g., sodium tripolyphosphate and sodium tripolyphospate hexahydrate,potassium tripolyphosphate, and mixed sodium and potassiumtripolyphosphate, etc.). It is contemplated that any suitable builderwill find use in the present disclosure, including those known in theart (See, e.g., EP2100949).

In some embodiments, builders for use herein include phosphate buildersand non-phosphate builders. In some embodiments, the builder is aphosphate builder. In some embodiments, the builder is a non-phosphatebuilder. If present, builders are used in a level of from 0.1% to 80%,or from 5% to 60%, or from 10% to 50%, by weight of the composition. Insome embodiments, the product comprises a mixture of phosphate andnon-phosphate builders. Suitable phosphate builders includemono-phosphates, di-phosphates, tri-polyphosphates oroligomeric-polyphosphates, including the alkali metal salts of thesecompounds, including the sodium salts. In some embodiments, a buildercan be sodium tripolyphosphate (STPP). Additionally, the composition cancomprise carbonate and/or citrate, preferably citrate that helps toachieve a neutral pH composition. Other suitable non-phosphate buildersinclude homopolymers and copolymers of polycarboxylic acids and theirpartially or completely neutralized salts, monomeric polycarboxylicacids and hydroxycarboxylic acids and their salts. In some embodiments,salts of the above mentioned compounds include ammonium and/or alkalimetal salts, i.e., lithium, sodium, and potassium salts, includingsodium salts. Suitable polycarboxylic acids include acyclic, alicyclic,hetero-cyclic and aromatic carboxylic acids, wherein in someembodiments, they can contain at least two carboxyl groups which are ineach case separated from one another by, in some instances, no more thantwo carbon atoms.

A detergent composition herein can comprise at least one chelatingagent. Suitable chelating agents include, but are not limited to copper,iron and/or manganese chelating agents and mixtures thereof. Inembodiments in which at least one chelating agent is used, thecomposition comprises from about 0.1% to about 15%, or even from about3.0% to about 10%, chelating agent by weight of the composition.

A detergent composition herein can comprise at least one deposition aid.Suitable deposition aids include, but are not limited to, polyethyleneglycol, polypropylene glycol, polycarboxylate, soil release polymerssuch as polytelephthalic acid, clays such as kaolinite, montmorillonite,atapulgite, illite, bentonite, halloysite, and mixtures thereof.

A detergent composition herein can comprise one or more dye transferinhibiting agents. Suitable polymeric dye transfer inhibiting agentsinclude, but are not limited to, polyvinylpyrrolidone polymers,polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles ormixtures thereof. Additional dye transfer inhibiting agents includemanganese phthalocyanine, peroxidases, polyvinylpyrrolidone polymers,polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles and/ormixtures thereof; chelating agents examples of which includeethylene-diamine-tetraacetic acid (EDTA); diethylene triamine pentamethylene phosphonic acid (DTPMP); hydroxy-ethane diphosphonic acid(HEDP); ethylenediamine N,N′-disuccinic acid (EDDS); methyl glycinediacetic acid (MGDA); diethylene triamine penta acetic acid (DTPA);propylene diamine tetracetic acid (PDT A); 2-hydroxypyridine-N-oxide(HPNO); or methyl glycine diacetic acid (MGDA); glutamic acidN,N-diacetic acid (N,N-dicarboxymethyl glutamic acid tetrasodium salt(GLDA); nitrilotriacetic acid (NTA); 4,5-dihydroxy-m-benzenedisulfonicacid; citric acid and any salts thereof;N-hydroxyethylethylenediaminetri-acetic acid (HEDTA),triethylenetetraaminehexaacetic acid (TTNA), N-hydroxyethyliminodiaceticacid (HEIDA), dihydroxyethylglycine (DHEG),ethylenediaminetetrapropionic acid (EDTP) and derivatives thereof, whichcan be used alone or in combination with any of the above. Inembodiments in which at least one dye transfer inhibiting agent is used,a composition herein may comprise from about 0.0001% to about 10%, fromabout 0.01% to about 5%, or even from about 0.1% to about 3%, by weightof the composition.

A detergent composition herein can comprise silicates. In some of theseembodiments, sodium silicates (e.g., sodium disilicate, sodiummetasilicate, and/or crystalline phyllosilicates) find use. In someembodiments, silicates are present at a level of from about 1% to about20% by weight of the composition. In some embodiments, silicates arepresent at a level of from about 5% to about 15% by weight of thecomposition.

A detergent composition herein can comprise dispersants. Suitablewater-soluble organic materials include, but are not limited to thehomo- or co-polymeric acids or their salts, in which the polycarboxylicacid comprises at least two carboxyl radicals separated from each otherby not more than two carbon atoms.

Any cellulase disclosed above is contemplated for use in the discloseddetergent compositions. Suitable cellulases include, but are not limitedto Humicola insolens cellulases (See, e.g., U.S. Pat. No. 4,435,307).Exemplary cellulases contemplated for such use are those having colorcare benefit for a textile. Examples of cellulases that provide a colorcare benefit are disclosed in EP0495257, EP0531372, EP531315,WO96/11262, WO96/29397, WO94/07998; WO98/12307; WO95/24471, WO98/08940,and U.S. Pat. Nos. 5,457,046, 5,686,593 and 5,763,254, all of which areincorporated herein by reference. Examples of commercially availablecellulases useful in a detergent include CELLUSOFT®, CELLUCLEAN®,CELLUZYME®, and CAREZYME® (Novo Nordisk A/S and Novozymes A/S);CLAZINASE®, PURADAX HA®, and REVITALENZ™ (DuPont IndustrialBiosciences); BIOTOUCH® (AB Enzymes); and KAC-500(B)™ (Kao Corporation).Additional cellulases are disclosed in, e.g., U.S. Pat. No. 7,595,182,U.S. Pat. No. 8,569,033, U.S. Pat. No. 7,138,263, U.S. Pat. No.3,844,890, U.S. Pat. No. 4,435,307, U.S. Pat. No. 4,435,307, andGB2095275.

A detergent composition herein may additionally comprise one or moreother enzymes in addition to at least one cellulase. Examples of otherenzymes include proteases, cellulases, hemicellulases, peroxidases,lipolytic enzymes (e.g., metallolipolytic enzymes), xylanases, lipases,phospholipases, esterases (e.g., arylesterase, polyesterase),perhydrolases, cutinases, pectinases, pectate lyases, mannanases,keratinases, reductases, oxidases (e.g., choline oxidase,phenoloxidase), phenoloxidases, lipoxygenases, ligninases, pullulanases,tannases, pentosanases, malanases, beta-glucanases, arabinosidases,hyaluronidases, chondroitinases, laccases, metalloproteinases,amadoriases, glucoamylases, alpha-amylases, beta-amylases,galactosidases, galactanases, catalases, carageenases, hyaluronidases,keratinases, lactases, ligninases, peroxidases, phosphatases,polygalacturonases, pullulanases, rhamnogalactouronases, tannases,transglutaminases, xyloglucanases, xylosidases, metalloproteases,arabinofuranosidases, phytases, isomerases, transferases and/or amylasesin any combination.

In some embodiments of the present disclosure, the detergentcompositions can comprise one or more enzymes, each at a level fromabout 0.00001% to about 10% by weight of the composition and the balanceof cleaning adjunct materials by weight of composition. In some otherembodiments, the detergent compositions also comprise each enzyme at alevel of about 0.0001% to about 10%, about 0.001% to about 5%, about0.001% to about 2%, about 0.005% to about 0.5%, enzyme by weight of thecomposition.

Suitable proteases include those of animal, vegetable or microbialorigin. In some embodiments, microbial proteases are used. In someembodiments, chemically or genetically modified mutants are included. Insome embodiments, the protease is a serine protease, preferably analkaline microbial protease or a trypsin-like protease. Examples ofalkaline proteases include subtilisins, especially those derived fromBacillus (e.g., subtilisin, lentus, amyloliquefaciens, subtilisinCarlsberg, subtilisin 309, subtilisin 147 and subtilisin 168).Additional examples include those mutant proteases described in U.S.Pat. Nos. RE34606, 5955340, 5700676, 6312936 and 6482628, all of whichare incorporated herein by reference. Additional protease examplesinclude, but are not limited to, trypsin (e.g., of porcine or bovineorigin), and the Fusarium protease described in WO89/06270. In someembodiments, commercially available protease enzymes include, but arenot limited to, MAXATASE®, MAXACAL™, MAXAPEM™, OPTICLEAN®, OPTIMASE®,PROPERASE®, PURAFECT®, PURAFECT® OXP, PURAMAX™, EXCELLASE™, PREFERENZ™proteases (e.g. P100, P110, P280), EFFECTENZ™ proteases (e.g. P1000,P1050, P2000), EXCELLENZ™ proteases (e.g. P1000), ULTIMASE®, andPURAFAST™ (Genencor); ALCALASE®, SAVINASE®, PRIMASE®, DURAZYM™,POLARZYME®, OVOZYME®, KANNASE®, LIQUANASE®, NEUTRASE®, RELASE® andESPERASE® (Novozymes); BLAP™ and BLAP™ variants (HenkelKommanditgesellschaft auf Aktien, Duesseldorf, Germany), and KAP (B.alkalophilus subtilisin; Kao Corp., Tokyo, Japan). Various proteases aredescribed in WO95/23221, WO92/21760, WO09/149200, WO09/149144,WO09/149145, WO11/072099, WO10/056640, WO10/056653, WO11/140364,WO12/151534, U.S. Pat. Publ. No. 2008/0090747, and U.S. Pat. Nos.5,801,039, 5,340,735, 5,500,364, 5,855,625, RE34606, 5955340, 5700676,6312936, 6482628, 8530219, and various other patents. In some furtherembodiments, neutral metalloproteases find use, including but notlimited to, the neutral metalloproteases described in WO1999014341,WO1999033960, WO1999014342, WO1999034003, WO2007044993, WO2009058303 andWO2009058661, all of which are incorporated herein by reference.Exemplary metalloproteases include nprE, the recombinant form of neutralmetalloprotease expressed in Bacillus subtilis (See e.g., WO07/044993),and PMN, the purified neutral metalloprotease from Bacillusamyloliquefaciens.

Suitable mannanases include, but are not limited to, those of bacterialor fungal origin. Chemically or genetically modified mutants areincluded in some embodiments. Various mannanases are known which finduse in the present disclosure (See, e.g., U.S. Pat. Nos. 6,566,114,6,602,842, and 6,440,991, all of which are incorporated herein byreference). Commercially available mannanases that find use in thepresent disclosure include, but are not limited to MANNASTAR®,PURABRITE™, and MANNAWAY®.

Suitable lipases include those of bacterial or fungal origin. Chemicallymodified, proteolytically modified, or protein engineered mutants areincluded. Examples of useful lipases include those from the generaHumicola (e.g., H. lanuginosa, EP258068 and EP305216; H. insolens,WO96/13580), Pseudomonas (e.g., P. alcaligenes or P. pseudoalcaligenes,EP218272; P. cepacia, EP331376; P. stutzeri, GB1372034; P. fluorescensand Pseudomonas sp. strain SD 705, WO95/06720 and WO96/27002; P.wisconsinensis, WO96/12012); and Bacillus (e.g., B. subtilis, Dartois etal., Biochemica et Biophysica Acta 1131:253-360; B. stearothermophilus,JP64/744992; B. pumilus, WO91/16422). Furthermore, a number of clonedlipases find use in some embodiments of the present disclosure,including but not limited to, Penicillium camembertii lipase (See,Yamaguchi et al., Gene 103:61-67 [1991]), Geotricum candidum lipase(See, Schimada et al., J. Biochem., 106:383-388 [1989]), and variousRhizopus lipases such as R. delemar lipase (See, Hass et al., Gene109:117-113 [1991]), a R. niveus lipase (Kugimiya et al., Biosci.Biotech. Biochem. 56:716-719 [1992]) and R. oryzae lipase. Additionallipases useful herein include, for example, those disclosed inWO92/05249, WO94/01541, WO95/35381, WO96/00292, WO95/30744, WO94/25578,WO95/14783, WO95/22615, WO97/04079, WO97/07202, EP407225 and EP260105.Other types of lipase polypeptide enzymes such as cutinases also finduse in some embodiments of the present disclosure, including but notlimited to, cutinase derived from Pseudomonas mendocina (See,WO88/09367), and cutinase derived from Fusarium solani pisi (See,WO90/09446). Examples of certain commercially available lipase enzymesuseful herein include M1 LIPASE™, LUMA FAST™, and LIPOMAX™ (Genencor);LIPEX®, LIPOLASE® and LIPOLASE® ULTRA (Novozymes); and LIPASE P™ “Amano”(Amano Pharmaceutical Co. Ltd., Japan).

Suitable polyesterases include, for example, those disclosed inWO01/34899, WO01/14629 and U.S. Pat. No. 6,933,140.

A detergent composition herein can also comprise 2,6-beta-D-fructanhydrolase, which is effective for removal/cleaning of certain biofilmspresent on household and/or industrial textiles/laundry.

Suitable amylases include, but are not limited to those of bacterial orfungal origin. Chemically or genetically modified mutants are includedin some embodiments. Amylases that find use in the present disclosure,include, but are not limited to, alpha-amylases obtained from B.licheniformis (See e.g., GB1296839). Additional suitable amylasesinclude those disclosed in W09510603, WO9526397, WO9623874, WO9623873,WO9741213, WO9919467, WO0060060, WO0029560, WO9923211, WO9946399,WO0060058, WO0060059, WO9942567, WO0114532, WO02092797, WO0166712,WO0188107, WO0196537, WO0210355, WO9402597, WO0231124, WO9943793,WO9943794, WO2004113551, WO2005001064, WO2005003311, WO0164852,WO2006063594, WO2006066594, WO2006066596, WO2006012899, WO2008092919,WO2008000825, WO2005018336, WO2005066338, WO2009140504, WO2005019443,WO2010091221, WO2010088447, WO0134784, WO2006012902, WO2006031554,WO2006136161, WO2008101894, WO2010059413, WO2011098531, WO2011080352,WO2011080353, WO2011080354, WO2011082425, WO2011082429, WO2011076123,WO2011087836, WO2011076897, WO94183314, WO9535382, WO9909183, WO9826078,WO9902702, WO9743424, WO9929876, WO9100353, WO9605295, WO9630481,WO9710342, WO2008088493, WO2009149419, WO2009061381, WO2009100102,WO2010104675, WO2010117511, and WO2010115021, all of which areincorporated herein by reference.

Suitable amylases include, for example, commercially available amylasessuch as STAINZYME®, STAINZYME PLUS®, NATALASE®, DURAMYL®, TERMAMYL®,TERMAMYL ULTRA®, FUNGAMYL® and BAN™ (Novo Nordisk NS and Novozymes NS);RAPIDASE®, POWERASE®, PURASTAR® and PREFERENZ™ (DuPont IndustrialBiosciences).

Suitable peroxidases/oxidases contemplated for use in the compositionsinclude those of plant, bacterial or fungal origin. Chemically modifiedor protein engineered mutants are included. Examples of peroxidasesuseful herein include those from the genus Coprinus (e.g., C. cinereus,WO93/24618, WO95/10602, and WO98/15257), as well as those referenced inWO2005056782, WO2007106293, WO2008063400, WO2008106214, andWO2008106215. Commercially available peroxidases useful herein include,for example, GUARDZYME™ (Novo Nordisk NS and Novozymes NS).

In some embodiments, peroxidases are used in combination with hydrogenperoxide or a source thereof (e.g., a percarbonate, perborate orpersulfate) in the compositions of the present disclosure. In somealternative embodiments, oxidases are used in combination with oxygen.Both types of enzymes are used for “solution bleaching” (i.e., toprevent transfer of a textile dye from a dyed fabric to another fabricwhen the fabrics are washed together in a wash liquor), preferablytogether with an enhancing agent (See e.g., WO94/12621 and WO95/01426).Suitable peroxidases/oxidases include, but are not limited to, those ofplant, bacterial or fungal origin. Chemically or genetically modifiedmutants are included in some embodiments.

Cellulase and/or other enzymes comprised in a detergent compositionherein may be stabilized using conventional stabilizing agents, e.g., apolyol such as propylene glycol or glycerol; a sugar or sugar alcohol;lactic acid; boric acid or a boric acid derivative (e.g., an aromaticborate ester).

A detergent composition herein may contain about 1 wt % to about 65 wt %of a detergent builder or complexing agent such as zeolite, diphosphate,triphosphate, phosphonate, citrate, nitrilotriacetic acid (NTA),ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaaceticacid (DTMPA), alkyl- or alkenylsuccinic acid, soluble silicates orlayered silicates (e.g., SKS-6 from Hoechst). A detergent may also beunbuilt, i.e., essentially free of detergent builder. Cellulase andoptionally other enzymes comprised in a detergent herein is/aretypically used with detergent ingredients that are compatible with thestability of the enzyme. Nonetheless, enzymes generally can be protectedagainst deleterious components by known forms of encapsulation (e.g.,granulation or sequestration in hydro gels).

A detergent composition in certain embodiments may comprise one or moreother types of polymers in addition to a poly alpha-1,3-glucan and/orpoly alpha-1,3-glucan ether compound. Examples of other types ofpolymers useful herein include carboxymethyl cellulose (CMC),poly(vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly(vinylalcohol) (PVA), polycarboxylates such as polyacrylates, maleic/acrylicacid copolymers and lauryl methacrylate/acrylic acid copolymers.

A detergent composition herein may contain a bleaching system. Forexample, a bleaching system can comprise an H₂O₂ source such asperborate or percarbonate, which may be combined with a peracid-formingbleach activator such as tetraacetylethylenediamine (TAED) ornonanoyloxybenzenesulfonate (NOBS). Alternatively, a bleaching systemmay comprise peroxyacids (e.g., amide, imide, or sulfone typeperoxyacids). Alternatively still, a bleaching system can be anenzymatic bleaching system comprising perhydrolase, for example, such asthe system described in WO2005/056783.

A detergent composition herein may also contain conventional detergentingredients such as fabric conditioners, clays, foam boosters, sudssuppressors, anti-corrosion agents, soil-suspending agents, anti-soilredeposition agents, dyes, bactericides, tarnish inhibiters, opticalbrighteners, or perfumes. The pH of a detergent composition herein(measured in aqueous solution at use concentration) is usually neutralor alkaline (e.g., pH of about 7.0 to about 11.0).

Particular forms of detergent compositions that can be adapted forpurposes disclosed herein are disclosed in, for example,US20090209445A1, US20100081598A1, U.S. Pat. No. 7,001,878B2,EP1504994B1, WO2001085888A2, WO2003089562A1, WO2009098659A1,WO2009098660A1, WO2009112992A1, WO2009124160A1, WO2009152031A1,WO2010059483A1, WO2010088112A1, WO2010090915A1, WO2010135238A1,WO2011094687A1, WO2011094690A1, WO2011127102A1, WO2011163428A1,WO2008000567A1, WO2006045391A1, WO2006007911A1, WO2012027404A1,EP1740690B1, WO2012059336A1, U.S. Pat. No. 6,730,646B1, WO2008087426A1,WO2010116139A1, and WO2012104613A1, all of which are incorporated hereinby reference.

Laundry detergent compositions herein can optionally be heavy duty (allpurpose) laundry detergent compositions. Exemplary heavy duty laundrydetergent compositions comprise a detersive surfactant (10%-40% wt/wt),including an anionic detersive surfactant (selected from a group oflinear or branched or random chain, substituted or unsubstituted alkylsulphates, alkyl sulphonates, alkyl alkoxylated sulphate, alkylphosphates, alkyl phosphonates, alkyl carboxylates, and/or mixturesthereof), and optionally non-ionic surfactant (selected from a group oflinear or branched or random chain, substituted or unsubstituted alkylalkoxylated alcohol, e.g., C8-C18 alkyl ethoxylated alcohols and/orC6-C12 alkyl phenol alkoxylates), where the weight ratio of anionicdetersive surfactant (with a hydrophilic index (Hlc) of from 6.0 to 9)to non-ionic detersive surfactant is greater than 1:1. Suitabledetersive surfactants also include cationic detersive surfactants(selected from a group of alkyl pyridinium compounds, alkyl quaternaryammonium compounds, alkyl quaternary phosphonium compounds, alkylternary sulphonium compounds, and/or mixtures thereof); zwitterionicand/or amphoteric detersive surfactants (selected from a group ofalkanolamine sulpho-betaines); ampholytic surfactants; semi-polarnon-ionic surfactants and mixtures thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally include, a surfactancy boosting polymer consisting ofamphiphilic alkoxylated grease cleaning polymers (selected from a groupof alkoxylated polymers having branched hydrophilic and hydrophobicproperties, such as alkoxylated polyalkylenimines in the range of 0.05wt %-10 wt %) and/or random graft polymers (typically comprising ofhydrophilic backbone comprising monomers selected from the groupconsisting of: unsaturated C1-C6 carboxylic acids, ethers, alcohols,aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride,saturated polyalcohols such as glycerol, and mixtures thereof; andhydrophobic side chain(s) selected from the group consisting of: C4-C25alkyl group, polypropylene, polybutylene, vinyl ester of a saturatedC1-C6 mono-carboxylic acid, C1-C6 alkyl ester of acrylic or methacrylicacid, and mixtures thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally include additional polymers such as soil release polymers(include anionically end-capped polyesters, for example SRP1, polymerscomprising at least one monomer unit selected from saccharide,dicarboxylic acid, polyol and combinations thereof, in random or blockconfiguration, ethylene terephthalate-based polymers and co-polymersthereof in random or block configuration, for example REPEL-O-TEX SF,SF-2 AND SRP6, TEXCARE SRA100, SRA300, SRN100, SRN170, SRN240, SRN300AND SRN325, MARLOQUEST SL), anti-redeposition polymers (0.1 wt % to 10wt %), include carboxylate polymers, such as polymers comprising atleast one monomer selected from acrylic acid, maleic acid (or maleicanhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid,citraconic acid, methylenemalonic acid, and any mixture thereof,vinylpyrrolidone homopolymer, and/or polyethylene glycol, molecularweight in the range of from 500 to 100,000 Da); and polymericcarboxylate (such as maleate/acrylate random copolymer or polyacrylatehomopolymer).

A detergent herein such as a heavy duty laundry detergent compositionmay optionally further include saturated or unsaturated fatty acids,preferably saturated or unsaturated C12-C24 fatty acids (0 wt % to 10 wt%); deposition aids in addition to a poly alpha-1,3-glucan ethercompound disclosed herein (examples for which include polysaccharides,cellulosic polymers, poly diallyl dimethyl ammonium halides (DADMAC),and co-polymers of DAD MAC with vinyl pyrrolidone, acrylamides,imidazoles, imidazolinium halides, and mixtures thereof, in random orblock configuration, cationic guar gum, cationic starch, cationicpolyacylamides, and mixtures thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally further include dye transfer inhibiting agents, examplesof which include manganese phthalocyanine, peroxidases,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles and/or mixtures thereof; chelating agents, examplesof which include ethylene-diamine-tetraacetic acid (EDTA), diethylenetriamine penta methylene phosphonic acid (DTPMP), hydroxy-ethanediphosphonic acid (HEDP), ethylenediamine N,N′-disuccinic acid (EDDS),methyl glycine diacetic acid (MGDA), diethylene triamine penta aceticacid (DTPA), propylene diamine tetracetic acid (PDTA),2-hydroxypyridine-N-oxide (HPNO), or methyl glycine diacetic acid(MGDA), glutamic acid N,N-diacetic acid (N,N-dicarboxymethyl glutamicacid tetrasodium salt (GLDA), nitrilotriacetic acid (NTA),4,5-dihydroxy-m-benzenedisulfonic acid, citric acid and any saltsthereof, N-hydroxyethylethylenediaminetriacetic acid (HEDTA),triethylenetetraaminehexaacetic acid (TTNA), N-hydroxyethyliminodiaceticacid (HEIDA), dihydroxyethylglycine (DHEG),ethylenediaminetetrapropionic acid (EDTP), and derivatives thereof.

A detergent herein such as a heavy duty laundry detergent compositionmay comprise active cellulase, and optionally one or more other types ofenzymes disclosed herein, each at about 0.01 wt % to about 0.03 wt %active enzyme. The composition may include an enzyme stabilizer, such asany of those disclosed herein.

A detergent herein such as a heavy duty laundry detergent compositionmay optionally include silicone or fatty-acid based suds suppressors;hueing dyes, calcium and magnesium cations, visual signalingingredients, anti-foam (0.001 wt % to about 4.0 wt %), and/or astructurant/thickener (0.01 wt % to 5 wt %) selected from the groupconsisting of diglycerides and triglycerides, ethylene glycoldistearate, microcrystalline cellulose, microfiber cellulose,biopolymers, xanthan gum, gellan gum, and mixtures thereof). Suchstructurant/thickener would be in addition to the one or more polyalpha-1,3-glucan compounds comprised in the detergent. A structurant canalso be referred to as a structural agent, structuring agent or externalstructurant. These terms can be used interchangeably.

A detergent herein can be in the form of a heavy duty dry/solid laundrydetergent composition, for example. Such a detergent may include: (i) adetersive surfactant, such as any anionic detersive surfactant disclosedherein, any non-ionic detersive surfactant disclosed herein, anycationic detersive surfactant disclosed herein, any zwitterionic and/oramphoteric detersive surfactant disclosed herein, any ampholyticsurfactant, any semi-polar non-ionic surfactant, and mixtures thereof;(ii) a builder, such as any phosphate-free builder (e.g., zeolitebuilders in the range of 0 wt % to less than 10 wt %), any phosphatebuilder (e.g., sodium tri-polyphosphate in the range of 0 wt % to lessthan 10 wt %), citric acid, citrate salts and nitrilotriacetic acid, anysilicate salt (e.g., sodium or potassium silicate or sodiummeta-silicate in the range of 0 wt % to less than 10 wt %); anycarbonate salt (e.g., sodium carbonate and/or sodium bicarbonate in therange of 0 wt % to less than 80 wt %), and mixtures thereof; (iii) ableaching agent, such as any photobleach (e.g., sulfonated zincphthalocyanines, sulfonated aluminum phthalocyanines, xanthenes dyes,and mixtures thereof), any hydrophobic or hydrophilic bleach activator(e.g., dodecanoyl oxybenzene sulfonate, decanoyl oxybenzene sulfonate,decanoyl oxybenzoic acid or salts thereof, 3,5,5-trimethy hexanoyloxybenzene sulfonate, tetraacetyl ethylene diamine-TAED,nonanoyloxybenzene sulfonate-NOBS, nitrile quats, and mixtures thereof),any source of hydrogen peroxide (e.g., inorganic perhydrate salts,examples of which include mono or tetra hydrate sodium salt ofperborate, percarbonate, persulfate, perphosphate, or persilicate), anypreformed hydrophilic and/or hydrophobic peracids (e.g., percarboxylicacids and salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, and mixtures thereof); and/or (iv)any other components such as a bleach catalyst (e.g., imine bleachboosters examples of which include iminium cations and polyions, iminiumzwitterions, modified amines, modified amine oxides, N-sulphonyl imines,N-phosphonyl imines, N-acyl imines, thiadiazole dioxides,perfluoroimines, cyclic sugar ketones, and mixtures thereof), and ametal-containing bleach catalyst (e.g., copper, iron, titanium,ruthenium, tungsten, molybdenum, or manganese cations along with anauxiliary metal cations such as zinc or aluminum and a sequestrate suchas EDTA, ethylenediaminetetra(methylenephosphonic acid).

Compositions disclosed herein can be in the form of a dishwashingdetergent composition. Examples of dishwashing detergents includeautomatic dishwashing detergents (typically used in dishwasher machines)and hand-washing dish detergents. A dishwashing detergent compositioncan be in any dry or liquid/aqueous form as disclosed herein, forexample. Components that may be included in certain embodiments of adishwashing detergent composition include, for example, one or more of aphosphate; oxygen- or chlorine-based bleaching agent; non-ionicsurfactant; alkaline salt (e.g., metasilicates, alkali metal hydroxides,sodium carbonate); any active enzyme disclosed herein in addition tocellulase; anti-corrosion agent (e.g., sodium silicate); anti-foamingagent; additives to slow down the removal of glaze and patterns fromceramics; perfume; anti-caking agent (in granular detergent); starch (intablet-based detergents); gelling agent (in liquid/gel baseddetergents); and/or sand (powdered detergents).

Dishwashing detergents such as an automatic dishwasher detergent orliquid dishwashing detergent can comprise (i) a non-ionic surfactant,including any ethoxylated non-ionic surfactant, alcohol alkoxylatedsurfactant, epoxy-capped poly(oxyalkylated) alcohol, or amine oxidesurfactant present in an amount from 0 to 10 wt %; (ii) a builder, inthe range of about 5-60 wt %, including any phosphate builder (e.g.,mono-phosphates, di-phosphates, tri-polyphosphates, otheroligomeric-polyphosphates, sodium tripolyphosphate-STPP), anyphosphate-free builder (e.g., amino acid-based compounds includingmethyl-glycine-diacetic acid [MGDA] and salts or derivatives thereof,glutamic-N,N-diacetic acid [GLDA] and salts or derivatives thereof,iminodisuccinic acid (IDS) and salts or derivatives thereof, carboxymethyl inulin and salts or derivatives thereof, nitrilotriacetic acid[NTA], diethylene triamine penta acetic acid [DTPA], B-alaninediaceticacid [B-ADA] and salts thereof), homopolymers and copolymers ofpoly-carboxylic acids and partially or completely neutralized saltsthereof, monomeric polycarboxylic acids and hydroxycarboxylic acids andsalts thereof in the range of 0.5 wt % to 50 wt %, orsulfonated/carboxylated polymers in the range of about 0.1 wt % to about50 wt %; (iii) a drying aid in the range of about 0.1 wt % to about 10wt % (e.g., polyesters, especially anionic polyesters, optionallytogether with further monomers with 3 to 6 functionalities—typicallyacid, alcohol or ester functionalities which are conducive topolycondensation, polycarbonate-, polyurethane- and/orpolyurea-polyorganosiloxane compounds or precursor compounds thereof,particularly of the reactive cyclic carbonate and urea type); (iv) asilicate in the range from about 1 wt % to about 20 wt % (e.g., sodiumor potassium silicates such as sodium disilicate, sodium meta-silicateand crystalline phyllosilicates); (v) an inorganic bleach (e.g.,perhydrate salts such as perborate, percarbonate, perphosphate,persulfate and persilicate salts) and/or an organic bleach (e.g.,organic peroxyacids such as diacyl- and tetraacylperoxides, especiallydiperoxydodecanedioic acid, diperoxytetradecanedioic acid, anddiperoxyhexadecanedioic acid); (vi) a bleach activator (e.g., organicperacid precursors in the range from about 0.1 wt % to about 10 wt %)and/or bleach catalyst (e.g., manganese triazacyclononane and relatedcomplexes; Co, Cu, Mn, and Fe bispyridylamine and related complexes; andpentamine acetate cobalt(III) and related complexes); (vii) a metal careagent in the range from about 0.1 wt % to 5 wt % (e.g., benzatriazoles,metal salts and complexes, and/or silicates); and/or (viii) any activeenzyme disclosed herein in addition to cellulase in the range from about0.01 to 5.0 mg of active enzyme per gram of automatic dishwashingdetergent composition, and an enzyme stabilizer component (e.g.,oligosaccharides, polysaccharides, and inorganic divalent metal salts).

Various examples of detergent formulations comprising cellulase and atleast one poly alpha-1,3-glucan ether compound (e.g., a carboxyalkylpoly alpha-1,3-glucan ether such as carboxymethyl poly alpha-1,3-glucan[CMG]) are disclosed below (1-19):

1) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 7-12 wt %; alcohol ethoxysulfate (e.g.,C12-18 alcohol, 1-2 ethylene oxide [EO]) or alkyl sulfate (e.g., C16-18)at about 1-4 wt %; alcohol ethoxylate (e.g., C14-15 alcohol) at about5-9 wt %; sodium carbonate at about 14-20 wt %; soluble silicate (e.g.,Na₂O 2SiO₂) at about 2-6 wt %; zeolite (e.g., NaAlSiO₄) at about 15-22wt %; sodium sulfate at about 0-6 wt %; sodium citrate/citric acid atabout 0-15 wt %; sodium perborate at about 11-18 wt %; TAED at about 2-6wt %; poly alpha-1,3-glucan ether (e.g. CMG) up to about 2 wt %; otherpolymers (e.g., maleic/acrylic acid copolymer, PVP, PEG) at about 0-3 wt%; cellulase and optionally other enzymes (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g., sudssuppressors, perfumes, optical brightener, photobleach) at about 0-5 wt%.

2) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 6-11 wt %; alcohol ethoxysulfate (e.g.,C12-18 alcohol, 1-2 EO) or alkyl sulfate (e.g., C16-18) at about 1-3 wt%; alcohol ethoxylate (e.g., C14-15 alcohol) at about 5-9 wt %; sodiumcarbonate at about 15-21 wt %; soluble silicate (e.g., Na₂O 2SiO₂) atabout 1-4 wt %; zeolite (e.g., NaAlSiO₄) at about 24-34 wt %; sodiumsulfate at about 4-10 wt %; sodium citrate/citric acid at about 0-15 wt%; sodium perborate at about 11-18 wt %; TAED at about 2-6 wt %; polyalpha-1,3-glucan ether (e.g. CMG) up to about 2 wt %; other polymers(e.g., maleic/acrylic acid copolymer, PVP, PEG) at about 1-6 wt %;cellulase and optionally other enzymes (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g., sudssuppressors, perfumes, optical brightener, photobleach) at about 0-5 wt%.

3) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 5-9 wt %; alcohol ethoxysulfate (e.g.,C12-18 alcohol, 7 EO) at about 7-14 wt %; soap as fatty acid (e.g.,C16-22 fatty acid) at about 1-3 wt %; sodium carbonate at about 10-17 wt%; soluble silicate (e.g., Na₂O 2SiO₂) at about 3-9 wt %; zeolite (e.g.,NaAlSiO₄) at about 23-33 wt %; sodium sulfate at about 0-4 wt %; sodiumperborate at about 8-16 wt %; TAED at about 2-8 wt %; phosphonate (e.g.,EDTMPA) at about 0-1 wt %; poly alpha-1,3-glucan ether (e.g. CMG) up toabout 2 wt %; other polymers (e.g., maleic/acrylic acid copolymer, PVP,PEG) at about 0-3 wt %; cellulase and optionally other enzymes(calculated as pure enzyme protein) at about 0.0001-0.1 wt %; and minoringredients (e.g., suds suppressors, perfumes, optical brightener) atabout 0-5 wt %.

4) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: linear alkylbenzenesulfonate(calculated as acid) at about 8-12 wt %; alcohol ethoxylate (e.g.,C12-18 alcohol, 7 EO) at about 10-25 wt %; sodium carbonate at about14-22 wt %; soluble silicate (e.g., Na₂O 2SiO₂) at about 1-5 wt %;zeolite (e.g., NaAlSiO₄) at about 25-35 wt %; sodium sulfate at about0-10 wt %; sodium perborate at about 8-16 wt %; TAED at about 2-8 wt %;phosphonate (e.g., EDTMPA) at about 0-1 wt %; poly alpha-1,3-glucanether (e.g. CMG) up to about 2 wt %; other polymers (e.g.,maleic/acrylic acid copolymer, PVP, PEG) at about 1-3 wt %; cellulaseand optionally other enzymes (calculated as pure enzyme protein) atabout 0.0001-0.1 wt %; and minor ingredients (e.g., suds suppressors,perfumes) at about 0-5 wt %.

5) An aqueous liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 15-21 wt %; alcoholethoxylate (e.g., C12-18 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 12-18 wt %; soap as fatty acid (e.g., oleic acid) at about 3-13 wt%; alkenylsuccinic acid (C12-14) at about 0-13 wt %; aminoethanol atabout 8-18 wt %; citric acid at about 2-8 wt %; phosphonate at about 0-3wt %; poly alpha-1,3-glucan ether (e.g. CMG) up to about 2 wt %; otherpolymers (e.g., PVP, PEG) at about 0-3 wt %; borate at about 0-2 wt %;ethanol at about 0-3 wt %; propylene glycol at about 8-14 wt %;cellulase and optionally other enzymes (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g.,dispersants, suds suppressors, perfume, optical brightener) at about 0-5wt %.

6) An aqueous structured liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 15-21 wt %; alcoholethoxylate (e.g., C12-18 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 3-9 wt %; soap as fatty acid (e.g., oleic acid) at about 3-10 wt%; zeolite (e.g., NaAlSiO₄) at about 14-22 wt %; potassium citrate about9-18 wt %; borate at about 0-2 wt %; poly alpha-1,3-glucan ether (e.g.CMG) up to about 2 wt %; other polymers (e.g., PVP, PEG) at about 0-3 wt%; ethanol at about 0-3 wt %; anchoring polymers (e.g., laurylmethacrylate/acrylic acid copolymer, molar ratio 25:1, MW 3800) at about0-3 wt %; glycerol at about 0-5 wt %; cellulase and optionally otherenzymes (calculated as pure enzyme protein) at about 0.0001-0.1 wt %;and minor ingredients (e.g., dispersants, suds suppressors, perfume,optical brightener) at about 0-5 wt %.

7) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: fatty alcohol sulfate at about5-10 wt %, ethoxylated fatty acid monoethanolamide at about 3-9 wt %;soap as fatty acid at about 0-3 wt %; sodium carbonate at about 5-10 wt%; soluble silicate (e.g., Na₂O 2SiO₂) at about 1-4 wt %; zeolite (e.g.,NaAlSiO₄) at about 20-40 wt %; sodium sulfate at about 2-8 wt %; sodiumperborate at about 12-18 wt %; TAED at about 2-7 wt %; polyalpha-1,3-glucan ether (e.g. CMG) up to about 2 wt %; other polymers(e.g., maleic/acrylic acid copolymer, PEG) at about 1-5 wt %; cellulaseand optionally other enzymes (calculated as pure enzyme protein) atabout 0.0001-0.1 wt %; and minor ingredients (e.g., optical brightener,suds suppressors, perfumes) at about 0-5 wt %.

8) A detergent composition formulated as a granulate comprising: linearalkylbenzenesulfonate (calculated as acid) at about 8-14 wt %;ethoxylated fatty acid monoethanolamide at about 5-11 wt %; soap asfatty acid at about 0-3 wt %; sodium carbonate at about 4-10 wt %;soluble silicate (e.g., Na₂O 2SiO₂) at about 1-4 wt %; zeolite (e.g.,NaAlSiO₄) at about 30-50 wt %; sodium sulfate at about 3-11 wt %; sodiumcitrate at about 5-12 wt %; poly alpha-1,3-glucan ether (e.g. CMG) up toabout 2 wt %; other polymers (e.g., PVP, maleic/acrylic acid copolymer,PEG) at about 1-5 wt %; cellulase and optionally other enzymes(calculated as pure enzyme protein) at about 0.0001-0.1 wt %; and minoringredients (e.g., suds suppressors, perfumes) at about 0-5 wt %.

9) A detergent composition formulated as a granulate comprising: linearalkylbenzenesulfonate (calculated as acid) at about 6-12 wt %; nonionicsurfactant at about 1-4 wt %; soap as fatty acid at about 2-6 wt %;sodium carbonate at about 14-22 wt %; zeolite (e.g., NaAlSiO₄) at about18-32 wt %; sodium sulfate at about 5-20 wt %; sodium citrate at about3-8 wt %; sodium perborate at about 4-9 wt %; bleach activator (e.g.,NOBS or TAED) at about 1-5 wt %; poly alpha-1,3-glucan ether (e.g. CMG)up to about 2 wt %; other polymers (e.g., polycarboxylate or PEG) atabout 1-5 wt %; cellulase and optionally other enzymes (calculated aspure enzyme protein) at about 0.0001-0.1 wt %; and minor ingredients(e.g., optical brightener, perfume) at about 0-5 wt %.

10) An aqueous liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 15-23 wt %; alcoholethoxysulfate (e.g., C12-15 alcohol, 2-3 EO) at about 8-15 wt %; alcoholethoxylate (e.g., C12-15 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 3-9 wt %; soap as fatty acid (e.g., lauric acid) at about 0-3 wt%; aminoethanol at about 1-5 wt %; sodium citrate at about 5-10 wt %;hydrotrope (e.g., sodium toluenesulfonate) at about 2-6 wt %; borate atabout 0-2 wt %; poly alpha-1,3-glucan ether (e.g. CMG) up to about 1 wt%; ethanol at about 1-3 wt %; propylene glycol at about 2-5 wt %;cellulase and optionally other enzymes (calculated as pure enzymeprotein) at about 0.0001-0.1 wt %; and minor ingredients (e.g.,dispersants, perfume, optical brighteners) at about 0-5 wt %.

11) An aqueous liquid detergent composition comprising: linearalkylbenzenesulfonate (calculated as acid) at about 20-32 wt %; alcoholethoxylate (e.g., C12-15 alcohol, 7 EO; or C12-15 alcohol, 5 EO) atabout 6-12 wt %; aminoethanol at about 2-6 wt %; citric acid at about8-14 wt %; borate at about 1-3 wt %; poly alpha-1,3-glucan ether (e.g.CMG) up to about 2 wt %; ethanol at about 1-3 wt %; propylene glycol atabout 2-5 wt %; other polymers (e.g., maleic/acrylic acid copolymer,anchoring polymer such as lauryl methacrylate/acrylic acid copolymer) atabout 0-3 wt %; glycerol at about 3-8 wt %; cellulase and optionallyother enzymes (calculated as pure enzyme protein) at about 0.0001-0.1 wt%; and minor ingredients (e.g., hydrotropes, dispersants, perfume,optical brighteners) at about 0-5 wt %.

12) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: anionic surfactant (e.g., linearalkylbenzenesulfonate, alkyl sulfate, alpha-olefinsulfonate, alpha-sulfofatty acid methyl esters, alkanesulfonates, soap) at about 25-40 wt %;nonionic surfactant (e.g., alcohol ethoxylate) at about 1-10 wt %;sodium carbonate at about 8-25 wt %; soluble silicate (e.g., Na₂O 2SiO₂)at about 5-15 wt %; sodium sulfate at about 0-5 wt %; zeolite (NaAlSiO₄)at about 15-28 wt %; sodium perborate at about 0-20 wt %; bleachactivator (e.g., TAED or NOBS) at about 0-5 wt %; poly alpha-1,3-glucanether (e.g. CMG) up to about 2 wt %; cellulase and optionally otherenzymes (calculated as pure enzyme protein) at about 0.0001-0.1 wt %;and minor ingredients (e.g., perfume, optical brighteners) at about 0-3wt %.

13) Detergent compositions as described in (1)-(12) above, but in whichall or part of the linear alkylbenzenesulfonate is replaced by C12-C18alkyl sulfate.

14) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: C12-C18 alkyl sulfate at about9-15 wt %; alcohol ethoxylate at about 3-6 wt %; polyhydroxy alkyl fattyacid amide at about 1-5 wt %; zeolite (e.g., NaAlSiO₄) at about 10-20 wt%; layered disilicate (e.g., SK56 from Hoechst) at about 10-20 wt %;sodium carbonate at about 3-12 wt %; soluble silicate (e.g., Na₂O 2SiO₂)at 0-6 wt %; sodium citrate at about 4-8 wt %; sodium percarbonate atabout 13-22 wt %; TAED at about 3-8 wt %; poly alpha-1,3-glucan ether(e.g. CMG) up to about 2 wt %; other polymers (e.g., polycarboxylatesand PVP) at about 0-5 wt %; cellulase and optionally other enzymes(calculated as pure enzyme protein) at about 0.0001-0.1 wt %; and minoringredients (e.g., optical brightener, photobleach, perfume, sudssuppressors) at about 0-5 wt %.

15) A detergent composition formulated as a granulate having a bulkdensity of at least 600 g/L comprising: C12-C18 alkyl sulfate at about4-8 wt %; alcohol ethoxylate at about 11-15 wt %; soap at about 1-4 wt%; zeolite MAP or zeolite A at about 35-45 wt %; sodium carbonate atabout 2-8 wt %; soluble silicate (e.g., Na₂O 2SiO₂) at 0-4 wt %; sodiumpercarbonate at about 13-22 wt %; TAED at about 1-8 wt %; polyalpha-1,3-glucan ether (e.g. CMG) up to about 3 wt %; other polymers(e.g., polycarboxylates and PVP) at about 0-3 wt %; cellulase andoptionally other enzymes (calculated as pure enzyme protein) at about0.0001-0.1 wt %; and minor ingredients (e.g., optical brightener,phosphonate, perfume) at about 0-3 wt %.

16) Detergent formulations as described in (1)-(15) above, but thatcontain a stabilized or encapsulated peracid, either as an additionalcomponent or as a substitute for an already specified bleach system(s).

17) Detergent compositions as described in (1), (3), (7), (9) and (12)above, but in which perborate is replaced by percarbonate.

18) Detergent compositions as described in (1), (3), (7), (9), (12),(14) and (15) above, but that additionally contain a manganese catalyst.A manganese catalyst, for example, is one of the compounds described byHage et al. (1994, Nature 369:637-639), which is incorporated herein byreference.

19) Detergent compositions formulated as a non-aqueous detergent liquidcomprising a liquid non-ionic surfactant (e.g., a linear alkoxylatedprimary alcohol), a builder system (e.g., phosphate), polyalpha-1,3-glucan ether (e.g. CMG), a cellulase and possibly otherenzymes, and alkali. The detergent may also comprise an anionicsurfactant and/or bleach system.

The example detergent formulations provided in 1-19 above mayalternatively contain, for example, minimally about 0.01-0.1 ppm totalcellulase protein, or about 0.1-10 ppb total cellulase protein (e.g.,less than 1 ppm), to maximally about 100, 200, 500, 1000, 2000, 3000,4000, or 5000 ppm total cellulase protein, for example.

It is believed that numerous commercially available detergentformulations can be adapted to include cellulase and a polyalpha-1,3-glucan ether compound. Examples include PUREX® ULTRAPACKS(Henkel), FINISH® QUANTUM (Reckitt Benckiser), CLOROX™ 2 PACKS (Clorox),OXICLEAN MAX FORCE POWER PAKS (Church & Dwight), TIDE® STAIN RELEASE,CASCADE® ACTIONPACS, and TIDE® PODS™ (Procter & Gamble).

Compositions disclosed herein can be in the form of an oral carecomposition. Examples of oral care compositions include dentifrices,toothpaste, mouth wash, mouth rinse, chewing gum, and edible strips thatprovide some form of oral care (e.g., treatment or prevention ofcavities [dental caries], gingivitis, plaque, tartar, and/or periodontaldisease). An oral care composition can also be for treating an “oralsurface”, which encompasses any soft or hard surface within the oralcavity including surfaces of the tongue, hard and soft palate, buccalmucosa, gums and dental surfaces. A “dental surface” herein is a surfaceof a natural tooth or a hard surface of artificial dentition including acrown, cap, filling, bridge, denture, or dental implant, for example.

One or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ethercompounds comprised in an oral care composition typically are providedtherein as a thickening agent and/or dispersion agent, which may beuseful to impart a desired consistency and/or mouth feel to thecomposition. An oral care composition herein can comprise about0.01-15.0 wt % (e.g., ˜0.1-10 wt % or ˜0.1-5.0 wt %, ˜0.1-2.0 wt %) ofone or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ethercompounds disclosed herein (e.g., a carboxyalkyl poly alpha-1,3-glucanether such as carboxymethyl poly alpha-1,3-glucan [CMG]), for example.One or more other thickening agents or dispersion agents can also beprovided in an oral care composition herein, such as a carboxyvinylpolymer, carrageenan (e.g., L-carrageenan), natural gum (e.g., karaya,xanthan, gum arabic, tragacanth), colloidal magnesium aluminum silicate,or colloidal silica, for example.

An oral care composition herein may be a toothpaste or other dentifrice,for example. Such compositions, as well as any other oral carecomposition herein, can additionally comprise, without limitation, oneor more of an anticaries agent, antimicrobial or antibacterial agent,anticalculus or tartar control agent, surfactant, abrasive, pH-modifyingagent, foam modulator, humectant, flavorant, sweetener,pigment/colorant, whitening agent, and/or other suitable components.Examples of oral care compositions to which cellulase and one or morepoly alpha-1,3-glucan ether compounds can be added are disclosed in U.S.Patent Appl. Publ. Nos. 2006/0134025, 2002/0022006 and 2008/0057007,which are incorporated herein by reference.

An anticaries agent herein can be an orally acceptable source offluoride ions. Suitable sources of fluoride ions include fluoride,monofluorophosphate and fluorosilicate salts as well as amine fluorides,including olaflur(N′-octadecyltrimethylendiamine-N,N,N′-tris(2-ethanol)-dihydrofluoride),for example. An anticaries agent can be present in an amount providing atotal of about 100-20000 ppm, about 200-5000 ppm, or about 500-2500 ppm,fluoride ions to the composition, for example. In oral care compositionsin which sodium fluoride is the sole source of fluoride ions, an amountof about 0.01-5.0 wt %, about 0.05-1.0 wt %, or about 0.1-0.5 wt %,sodium fluoride can be present in the composition, for example.

An antimicrobial or antibacterial agent suitable for use in an oral carecomposition herein includes, for example, phenolic compounds (e.g.,4-allylcatechol; p-hydroxybenzoic acid esters such as benzylparaben,butylparaben, ethylparaben, methylparaben and propylparaben;2-benzylphenol; butylated hydroxyanisole; butylated hydroxytoluene;capsaicin; carvacrol; creosol; eugenol; guaiacol; halogenatedbisphenolics such as hexachlorophene and bromochlorophene;4-hexylresorcinol; 8-hydroxyquinoline and salts thereof; salicylic acidesters such as menthyl salicylate, methyl salicylate and phenylsalicylate; phenol; pyrocatechol; salicylanilide; thymol; halogenateddiphenylether compounds such as triclosan and triclosan monophosphate),copper (II) compounds (e.g., copper (II) chloride, fluoride, sulfate andhydroxide), zinc ion sources (e.g., zinc acetate, citrate, gluconate,glycinate, oxide, and sulfate), phthalic acid and salts thereof (e.g.,magnesium monopotassium phthalate), hexetidine, octenidine,sanguinarine, benzalkonium chloride, domiphen bromide, alkylpyridiniumchlorides (e.g. cetylpyridinium chloride, tetradecylpyridinium chloride,N-tetradecyl-4-ethylpyridinium chloride), iodine, sulfonamides,bisbiguanides (e.g., alexidine, chlorhexidine, chlorhexidinedigluconate), piperidino derivatives (e.g., delmopinol, octapinol),magnolia extract, grapeseed extract, rosemary extract, menthol,geraniol, citral, eucalyptol, antibiotics (e.g., augmentin, amoxicillin,tetracycline, doxycycline, minocycline, metronidazole, neomycin,kanamycin, clindamycin), and/or any antibacterial agents disclosed inU.S. Pat. No. 5,776,435, which is incorporated herein by reference. Oneor more antimicrobial agents can optionally be present at about 0.01-10wt % (e.g., 0.1-3 wt %), for example, in the disclosed oral carecomposition.

An anticalculus or tartar control agent suitable for use in an oral carecomposition herein includes, for example, phosphates and polyphosphates(e.g., pyrophosphates), polyaminopropanesulfonic acid (AMPS), zinccitrate trihydrate, polypeptides (e.g., polyaspartic and polyglutamicacids), polyolefin sulfonates, polyolefin phosphates, diphosphonates(e.g., azacycloalkane-2,2-diphosphonates such asazacycloheptane-2,2-diphosphonic acid), N-methylazacyclopentane-2,3-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonicacid (EHDP), ethane-1-amino-1,1-diphosphonate, and/or phosphonoalkanecarboxylic acids and salts thereof (e.g., their alkali metal andammonium salts). Useful inorganic phosphate and polyphosphate saltsinclude, for example, monobasic, dibasic and tribasic sodium phosphates,sodium tripolyphosphate, tetrapolyphosphate, mono-, di-, tri- andtetra-sodium pyrophosphates, disodium dihydrogen pyrophosphate, sodiumtrimetaphosphate, sodium hexametaphosphate, or any of these in whichsodium is replaced by potassium or ammonium. Other useful anticalculusagents in certain embodiments include anionic polycarboxylate polymers(e.g., polymers or copolymers of acrylic acid, methacrylic, and maleicanhydride such as polyvinyl methyl ether/maleic anhydride copolymers).Still other useful anticalculus agents include sequestering agents suchas hydroxycarboxylic acids (e.g., citric, fumaric, malic, glutaric andoxalic acids and salts thereof) and aminopolycarboxylic acids (e.g.,EDTA). One or more anticalculus or tartar control agents can optionallybe present at about 0.01-50 wt % (e.g., about 0.05-25 wt % or about0.1-15 wt %), for example, in the disclosed oral care composition.

A surfactant suitable for use in an oral care composition herein may beanionic, non-ionic, or amphoteric, for example. Suitable anionicsurfactants include, without limitation, water-soluble salts of C₈₋₂₀alkyl sulfates, sulfonated monoglycerides of C₈₋₂₀ fatty acids,sarcosinates, and taurates. Examples of anionic surfactants includesodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodiumlauryl sarcosinate, sodium lauryl isoethionate, sodium laurethcarboxylate and sodium dodecyl benzenesulfonate. Suitable non-ionicsurfactants include, without limitation, poloxamers, polyoxyethylenesorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates,tertiary amine oxides, tertiary phosphine oxides, and dialkylsulfoxides. Suitable amphoteric surfactants include, without limitation,derivatives of C₈₋₂₀ aliphatic secondary and tertiary amines having ananionic group such as a carboxylate, sulfate, sulfonate, phosphate orphosphonate. An example of a suitable amphoteric surfactant iscocoamidopropyl betaine. One or more surfactants are optionally presentin a total amount of about 0.01-10 wt % (e.g., about 0.05-5.0 wt % orabout 0.1-2.0 wt %), for example, in the disclosed oral carecomposition.

An abrasive suitable for use in an oral care composition herein mayinclude, for example, silica (e.g., silica gel, hydrated silica,precipitated silica), alumina, insoluble phosphates, calcium carbonate,and resinous abrasives (e.g., a urea-formaldehyde condensation product).Examples of insoluble phosphates useful as abrasives herein areorthophosphates, polymetaphosphates and pyrophosphates, and includedicalcium orthophosphate dihydrate, calcium pyrophosphate, beta-calciumpyrophosphate, tricalcium phosphate, calcium polymetaphosphate andinsoluble sodium polymetaphosphate. One or more abrasives are optionallypresent in a total amount of about 5-70 wt % (e.g., about 10-56 wt % orabout 15-30 wt %), for example, in the disclosed oral care composition.The average particle size of an abrasive in certain embodiments is about0.1-30 microns (e.g., about 1-20 microns or about 5-15 microns).

An oral care composition in certain embodiments may comprise at leastone pH-modifying agent. Such agents may be selected to acidify, makemore basic, or buffer the pH of a composition to a pH range of about2-10 (e.g., pH ranging from about 2-8, 3-9, 4-8, 5-7, 6-10, or 7-9).Examples of pH-modifying agents useful herein include, withoutlimitation, carboxylic, phosphoric and sulfonic acids; acid salts (e.g.,monosodium citrate, disodium citrate, monosodium malate); alkali metalhydroxides (e.g. sodium hydroxide, carbonates such as sodium carbonate,bicarbonates, sesquicarbonates); borates; silicates; phosphates (e.g.,monosodium phosphate, trisodium phosphate, pyrophosphate salts); andimidazole.

A foam modulator suitable for use in an oral care composition herein maybe a polyethylene glycol (PEG), for example. High molecular weight PEGsare suitable, including those having an average molecular weight ofabout 200000-7000000 (e.g., about 500000-5000000 or about1000000-2500000), for example. One or more PEGs are optionally presentin a total amount of about 0.1-10 wt % (e.g. about 0.2-5.0 wt % or about0.25-2.0 wt %), for example, in the disclosed oral care composition.

An oral care composition in certain embodiments may comprise at leastone humectant. A humectant in certain embodiments may be a polyhydricalcohol such as glycerin, sorbitol, xylitol, or a low molecular weightPEG. Most suitable humectants also may function as a sweetener herein.One or more humectants are optionally present in a total amount of about1.0-70 wt % (e.g., about 1.0-50 wt %, about 2-25 wt %, or about 5-15 wt%), for example, in the disclosed oral care composition.

A natural or artificial sweetener may optionally be comprised in an oralcare composition herein. Examples of suitable sweeteners includedextrose, sucrose, maltose, dextrin, invert sugar, mannose, xylose,ribose, fructose, levulose, galactose, corn syrup (e.g., high fructosecorn syrup or corn syrup solids), partially hydrolyzed starch,hydrogenated starch hydrolysate, sorbitol, mannitol, xylitol, maltitol,isomalt, aspartame, neotame, saccharin and salts thereof,dipeptide-based intense sweeteners, and cyclamates. One or moresweeteners are optionally present in a total amount of about 0.005-5.0wt %, for example, in the disclosed oral care composition.

A natural or artificial flavorant may optionally be comprised in an oralcare composition herein. Examples of suitable flavorants includevanillin; sage; marjoram; parsley oil; spearmint oil; cinnamon oil; oilof wintergreen (methylsalicylate); peppermint oil; clove oil; bay oil;anise oil; eucalyptus oil; citrus oils; fruit oils; essences such asthose derived from lemon, orange, lime, grapefruit, apricot, banana,grape, apple, strawberry, cherry, or pineapple; bean- and nut-derivedflavors such as coffee, cocoa, cola, peanut, or almond; and adsorbed andencapsulated flavorants. Also encompassed within flavorants herein areingredients that provide fragrance and/or other sensory effect in themouth, including cooling or warming effects. Such ingredients include,without limitation, menthol, menthyl acetate, menthyl lactate, camphor,eucalyptus oil, eucalyptol, anethole, eugenol, cassia, oxanone,Irisone®, propenyl guaiethol, thymol, linalool, benzaldehyde,cinnamaldehyde, N-ethyl-p-menthan-3-carboxamine,N,2,3-trimethyl-2-isopropylbutanamide, 3-(1-menthoxy)-propane-1,2-diol,cinnamaldehyde glycerol acetal (CGA), and menthone glycerol acetal(MGA). One or more flavorants are optionally present in a total amountof about 0.01-5.0 wt % (e.g., about 0.1-2.5 wt %), for example, in thedisclosed oral care composition.

An oral care composition in certain embodiments may comprise at leastone bicarbonate salt. Any orally acceptable bicarbonate can be used,including alkali metal bicarbonates such as sodium or potassiumbicarbonate, and ammonium bicarbonate, for example. One or morebicarbonate salts are optionally present in a total amount of about0.1-50 wt % (e.g., about 1-20 wt %), for example, in the disclosed oralcare composition.

An oral care composition in certain embodiments may comprise at leastone whitening agent and/or colorant. A suitable whitening agent is aperoxide compound such as any of those disclosed in U.S. Pat. No.8,540,971, which is incorporated herein by reference. Suitable colorantsherein include pigments, dyes, lakes and agents imparting a particularluster or reflectivity such as pearling agents, for example. Specificexamples of colorants useful herein include talc; mica; magnesiumcarbonate; calcium carbonate; magnesium silicate; magnesium aluminumsilicate; silica; titanium dioxide; zinc oxide; red, yellow, brown andblack iron oxides; ferric ammonium ferrocyanide; manganese violet;ultramarine; titaniated mica; and bismuth oxychloride. One or morecolorants are optionally present in a total amount of about 0.001-20 wt% (e.g., about 0.01-10 wt % or about 0.1-5.0 wt %), for example, in thedisclosed oral care composition.

Additional components that can optionally be included in an oralcomposition herein include enzymes other than cellulase, vitamins, andanti-adhesion agents, for example. Enzymes such as proteases can beadded for anti-stain and other effects in certain embodiments. Examplesof vitamins useful herein include vitamin C, vitamin E, vitamin B5, andfolic acid. Examples of suitable anti-adhesion agents include solbrol,ficin, and quorum-sensing inhibitors.

The present disclosure also concerns a method for preparing an aqueouscomposition. This method comprises contacting one or more polyalpha-1,3-glucan ether compounds disclosed herein with an aqueouscomposition. The poly alpha-1,3-glucan ether compound(s) used in thismethod is represented by the structure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be an H or an organic group. Furthermore, the polyalpha-1,3-glucan ether compound has a degree of substitution with theorganic group of about 0.05 to about 3.0. An aqueous compositionproduced by this method can comprise one or more cellulase enzymes.

In certain embodiments of the preparation method, the (i) the viscosityof the aqueous composition is increased by the poly alpha-1,3-glucanether compound, and/or (ii) the shear thinning behavior or the shearthickening behavior of the aqueous composition is increased by the polyalpha-1,3-glucan ether compound. The viscosity of an aqueous compositionbefore the contacting step, measured at about 20-25° C., can be about0-10000 cPs (or any integer between 0-10000 cPs), for example. Since theaqueous composition can be a hydrocolloid or the like in certainembodiments, it should be apparent that the method can be used toincrease the viscosity of aqueous compositions that are already viscous.

Contacting a poly alpha-1,3-glucan ether compound disclosed herein withan aqueous composition increases the viscosity of the aqueouscomposition in certain embodiments. This increase in viscosity can be anincrease of at least about 1%, 10%, 100%, 1000%, 100000%, or 1000000%(or any integer between 1% and 1000000%), for example, compared to theviscosity of the aqueous composition before the contacting step. Itshould be apparent that very large percent increases in viscosity can beobtained with the disclosed method when the aqueous composition haslittle to no viscosity before the contacting step.

Contacting a poly alpha-1,3-glucan ether compound disclosed herein withan aqueous composition increases the shear thinning behavior or theshear thickening behavior of the aqueous composition in certainembodiments. Thus, a poly alpha-1,3-glucan ether compound rheologicallymodifies the aqueous composition in these embodiments. The increase inshear thinning or shear thickening behavior can be an increase of atleast about 1%, 10%, 100%, 1000%, 100000%, or 1000000% (or any integerbetween 1% and 1000000%), for example, compared to the shear thinning orshear thickening behavior of the aqueous composition before thecontacting step. It should be apparent that very large percent increasesin rheologic modification can be obtained with the disclosed method whenthe aqueous composition has little to no rheologic behavior before thecontacting step.

The contacting step in the disclosed method of preparing an aqueouscomposition can be performed by mixing or dissolving a polyalpha-1,3-glucan ether compound(s) disclosed herein in the aqueouscomposition by any means known in the art. For example, mixing ordissolving can be performed manually or with a machine (e.g., industrialmixer or blender, orbital shaker, stir plate, homogenizer, sonicator,bead mill). Mixing or dissolving can comprise a homogenization step incertain embodiments. Homogenization (as well as any other type ofmixing) can be performed for about 5 to 60, 5 to 30, 10 to 60, 10 to 30,5 to 15, or 10 to 15 seconds (or any integer between 5 and 60 seconds),or longer periods of time as necessary to mix a poly alpha-1,3-glucanether compound with the aqueous composition. A homogenizer can be usedat about 5000 to 30000 rpm, 10000 to 30000 rpm, 15000 to 30000 rpm,15000 to 25000 rpm, or 20000 rpm (or any integer between 5000 and 30000rpm), for example.

After a poly alpha-1,3-glucan ether compound is mixed with or dissolvedinto an aqueous composition, the resulting aqueous composition may befiltered, or may not be filtered. For example, an aqueous compositionprepared with a homogenization step may or may not be filtered.

An aqueous composition prepared by the disclosed preparation methodcomprises one or more active cellulase enzymes. A cellulase can be (i)comprised in the aqueous composition prior to the contacting step, or(ii) added to the aqueous composition during or after the contactingstep. For instances when a poly alpha-1,3-glucan ether compound iscontacted with an aqueous composition already containing a cellulase, itwould be known in the art how to mix or dissolve the ether compoundwithout significantly affecting cellulase activity. Cellulase and polyalpha-1,3-glucan ether can simultaneously be contacted with an aqueouscomposition, if desired. For example, cellulase and polyalpha-1,3-glucan ether may be comprised together within a drycomposition (e.g., laundry detergent powder) that is added to an aqueouscomposition. Alternatively, cellulase may be added to an aqueouscomposition which already comprises one or more poly alpha-1,3-glucanether compounds.

Examples of cellulase enzymes, poly alpha-1,3-glucan ether compounds,and concentrations of each of these components, suitable for thepreparation method are disclosed herein.

Certain embodiments of a method of preparing an aqueous composition canbe used to prepare an aqueous composition disclosed herein, such as ahousehold product (e.g., laundry detergent, fabric softener, dishwasherdetergent), personal care product (e.g., a water-containing dentifricesuch as toothpaste), or industrial product.

The present disclosure also concerns a method of treating a material.This method comprises contacting a material with an aqueous compositioncomprising at least one cellulase and at least one poly alpha-1,3-glucanether compound disclosed herein. A poly alpha-1,3-glucan ethercompound(s) used in this method is represented by the structure:

Regarding the formula of this structure, n can be at least 6, and each Rcan independently be an H or an organic group. Furthermore, the polyalpha-1,3-glucan ether compound has a degree of substitution with theorganic group of about 0.05 to about 3.0.

A material contacted with an aqueous composition in a contacting methodherein can comprise a fabric in certain embodiments. A fabric herein cancomprise natural fibers, synthetic fibers, semi-synthetic fibers, or anycombination thereof. A semi-synthetic fiber herein is produced usingnaturally occurring material that has been chemically derivatized, anexample of which is rayon. Non-limiting examples of fabric types hereininclude fabrics made of (i) cellulosic fibers such as cotton (e.g.,broadcloth, canvas, chambray, chenille, chintz, corduroy, cretonne,damask, denim, flannel, gingham, jacquard, knit, matelassé, oxford,percale, poplin, plisse, sateen, seersucker, sheers, terry cloth,velvet), rayon (e.g., viscose, modal, lyocell), linen, and Tencel®; (ii)proteinaceous fibers such as silk, wool and related mammalian fibers;(iii) synthetic fibers such as polyester, acrylic, nylon, and the like;(iv) long vegetable fibers from jute, flax, ramie, coir, kapok, sisal,henequen, abaca, hemp and sunn; and (v) any combination of a fabric of(i)-(iv). Fabric comprising a combination of fiber types (e.g., naturaland synthetic) include those with both a cotton fiber and polyester, forexample. Materials/articles containing one or more fabrics hereininclude, for example, clothing, curtains, drapes, upholstery, carpeting,bed linens, bath linens, tablecloths, sleeping bags, tents, carinteriors, etc. Other materials comprising natural and/or syntheticfibers include, for example, non-woven fabrics, paddings, paper, andfoams.

An aqueous composition that is contacted with a fabric can be, forexample, a fabric care composition (e.g., laundry detergent, fabricsoftener). Thus, a treatment method in certain embodiments can beconsidered a fabric care method or laundry method if employing a fabriccare composition therein. A fabric care composition herein can effectone or more of the following fabric care benefits (i.e., surfacesubstantive effects): wrinkle removal, wrinkle reduction, wrinkleresistance, fabric wear reduction, fabric wear resistance, fabricpilling reduction, fabric color maintenance, fabric color fadingreduction, fabric color restoration, fabric soiling reduction, fabricsoil release, fabric shape retention, fabric smoothness enhancement,anti-redeposition of soil on fabric, anti-greying of laundry, improvedfabric hand/handle, and/or fabric shrinkage reduction.

Examples of conditions (e.g., time, temperature, wash/rinse volumes) forconducting a fabric care method or laundry method herein are disclosedin WO1997/003161 and U.S. Pat. Nos. 4,794,661, 4,580,421 and 5,945,394,which are incorporated herein by reference. In other examples, amaterial comprising fabric can be contacted with an aqueous compositionherein: (i) for at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90,100, 110, or 120 minutes; (ii) at a temperature of at least about 10,15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95°C. (e.g., for laundry wash or rinse: a “cold” temperature of about15-30° C., a “warm” temperature of about 30-50° C., a “hot” temperatureof about 50-95° C.); (iii) at a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10,11, or 12 (e.g., pH range of about 2-12, or about 3-11); (iv) at a salt(e.g., NaCl) concentration of at least about 0.5, 1.0, 1.5, 2.0, 2.5,3.0, 3.5, or 4.0 wt %; or any combination of (i)-(iv).

The contacting step in a fabric care method or laundry method cancomprise any of washing, soaking, and/or rinsing steps, for example.Contacting a material or fabric in still further embodiments can beperformed by any means known in the art, such as dissolving, mixing,shaking, spraying, treating, immersing, flushing, pouring on or in,combining, painting, coating, applying, affixing to, and/orcommunicating an effective amount of a poly alpha-1,3-glucan ethercompound herein with the fabric or material. In still furtherembodiments, contacting may be used to treat a fabric to provide asurface substantive effect. As used herein, the term “fabric hand” or“handle” refers to a person's tactile sensory response towards fabricwhich may be physical, physiological, psychological, social or anycombination thereof. In one embodiment, the fabric hand may be measuredusing a PhabrOmeter® System for measuring relative hand value (availablefrom Nu Cybertek, Inc. Davis, Calif.) (American Association of TextileChemists and Colorists (AATCC test method “202-2012, Relative Hand Valueof Textiles: Instrumental Method”)).

In certain embodiments of treating a material comprising fabric, a polyalpha-1,3-glucan ether compound component(s) of the aqueous compositionadsorbs to the fabric. This feature is believed to render polyalpha-1,3-glucan ether compounds (e.g., anionic glucan ether compoundssuch as carboxymethyl poly-alpha-1,3-glucan) useful as anti-redepositionagents and/or anti-greying agents in fabric care compositions disclosedherein (in addition to their viscosity-modifying effect). Ananti-redeposition agent or anti-greying agent herein helps keep soilfrom redepositing onto clothing in wash water after the soil has beenremoved. Carboxymethyl cellulose (CMC) has typically been used as ananti-redeposition agent in laundry detergents. However, CMC is notstable to cellulase and is thus less useful in detergents containingcellulase (e.g., cellulase that has been directly added to detergent,and/or background cellulase activity associated with a different type ofenzyme added to detergent). Poly alpha-1,3-glucan ether compounds, sincethey are both stable to cellulase and able to adsorb to fabric surfaces,are contemplated to be superior substitutes for CMC and other celluloseether compounds in fabric care compositions containing cellulase. Thissuperiority is also due in part to the cellulase-resistantviscosity-modifying effect of poly alpha-1,3-glucan ether compounds. Itis further contemplated that adsorption of one or more polyalpha-1,3-glucan ether compounds herein to a fabric enhances mechanicalproperties of the fabric.

The below Examples demonstrate that poly alpha-1,3-glucan ethercompounds such as carboxymethyl poly alpha-1,3-glucan adsorb to bothnatural (cotton, cretonne) and synthetic (polyester) fabrics, as well asa blend thereof (polyester/cretonne). This result is notable given thatcarboxymethyl cellulose (CMC) does not absorb to, or only poorly adsorbsto, polyester and polyester/cotton blends (see European Pat. Appl. Publ.No. EP0035478, for example). Thus, in certain embodiments of a treatmentmethod herein, an anionic poly alpha-1,3-glucan ether compound (e.g.,carboxyalkyl poly alpha-1,3-glucan such as carboxymethyl polyalpha-1,3-glucan) adsorbs to material comprising natural fiber (e.g.cotton) and/or synthetic fiber (e.g., polyester). Such adsorption of ananionic poly alpha-1,3-glucan ether compound can be at least about 20%,30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 120%, 140%, 160%, 180%, or 200%greater than the adsorption of the same glucan ether to a cotton fabric(e.g., cretonne), for example. Also, such adsorption may optionally beunder conditions of about 1-3 or 1-4 wt % salt (e.g., NaCl), and/or a pHof about 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5,9.0, or 9.5, for example.

Adsorption of a poly alpha-1,3-glucan ether compound to a fabric hereincan be measured following the methodology disclosed in the belowExamples, for example. Alternatively, adsorption can be measured using acolorimetric technique (e.g., Dubois et al., 1956, Anal. Chem.28:350-356; Zemlji{hacek over (c)} et al., 2006, Lenzinger Berichte85:68-76; both incorporated herein by reference) or any other methodknown in the art.

Other materials that can be contacted in the above treatment methodinclude surfaces that can be treated with a dish detergent (e.g.,automatic dishwashing detergent or hand dish detergent). Examples ofsuch materials include surfaces of dishes, glasses, pots, pans, bakingdishes, utensils and flatware made from ceramic material, china, metal,glass, plastic (e.g., polyethylene, polypropylene, polystyrene, etc.)and wood (collectively referred to herein as “tableware”). Thus, thetreatment method in certain embodiments can be considered a dishwashingmethod or tableware washing method, for example. Examples of conditions(e.g., time, temperature, wash volume) for conducting a dishwashing ortableware washing method herein are disclosed in U.S. Pat. No.8,575,083, which is incorporated herein by reference. In other examples,a tableware article can be contacted with an aqueous composition hereinunder a suitable set of conditions such as any of those disclosed abovewith regard to contacting a fabric-comprising material.

Other materials that can be contacted in the above treatment methodinclude oral surfaces such as any soft or hard surface within the oralcavity including surfaces of the tongue, hard and soft palate, buccalmucosa, gums and dental surfaces (e.g., natural tooth or a hard surfaceof artificial dentition such as a crown, cap, filling, bridge, denture,or dental implant). Thus, a treatment method in certain embodiments canbe considered an oral care method or dental care method, for example.Conditions (e.g., time, temperature) for contacting an oral surface withan aqueous composition herein should be suitable for the intendedpurpose of making such contact. Other surfaces that can be contacted ina treatment method also include a surface of the integumentary systemsuch as skin, hair or nails.

Thus, certain embodiments herein concern material (e.g., fabric) thatcomprises a poly alpha-1,3-glucan ether compound herein. Such materialcan be produced following a material treatment method as disclosed, forexample. A material may comprise a glucan ether compound in certainembodiments if the compound is adsorbed to, or otherwise in contactwith, the surface of the material.

Certain embodiments of a method of treating a material herein furthercomprise a drying step, in which a material is dried after beingcontacted with the aqueous composition. A drying step can be performeddirectly after the contacting step, or following one or more additionalsteps that might follow the contacting step (e.g., drying of a fabricafter being rinsed, in water for example, following a wash in an aqueouscomposition herein). Drying can be performed by any of several meansknown in the art, such as air drying (e.g., ˜20-25° C.), or at atemperature of at least about 30, 40, 50, 60, 70, 80, 90, 100, 120, 140,160, 170, 175, 180, or 200° C., for example. A material that has beendried herein typically has less than 3, 2, 1, 0.5, or 0.1 wt % watercomprised therein. Fabric is a preferred material for conducting anoptional drying step.

An aqueous composition used in a treatment method herein can be anyaqueous composition disclosed herein, such as in the above embodimentsor in the below Examples. Thus, the cellulase and poly alpha-1,3-glucanether components of an aqueous composition can be any as disclosedherein. Examples of aqueous compositions are detergents (e.g., laundrydetergent or dish detergent) and water-containing dentifrices such astoothpaste.

The embodiments disclosed above comprise one or more cellulase enzymes.In alternative embodiments, any of the above compositions or methods canlack a cellulase enzyme or can comprise no added cellulase enzyme.

Poly alpha-1,3-glucan ether compounds useful for preparing compositionsdisclosed herein can be prepared as disclosed in U.S. Appl. Publ. No.2014/0179913 (incorporated herein by reference), for example. Inaddition, poly alpha-1,3-glucan ether compounds herein can be producedby a method comprising: contacting poly alpha-1,3-glucan in a reactionunder alkaline conditions with at least one etherification agentcomprising an organic group, wherein the organic group is etherified tothe poly alpha-1,3-glucan thereby producing a poly alpha-1,3-glucanether compound represented by the structure:

wherein

-   (i) n is at least 6,-   (ii) each R is independently an H or an organic group, and-   (iii) the compound has a degree of substitution with the organic    group of about 0.05 to about 3.0.    A poly alpha-1,3-glucan ether produced by this method can optionally    be isolated. This method can be considered to comprise an    etherification reaction.

The following steps can be taken to prepare the above etherificationreaction. Poly alpha-1,3-glucan can be contacted with a solvent and oneor more alkali hydroxides to provide a solution or mixture. The alkalineconditions of the reaction can thus comprise an alkali hydroxidesolution. The pH of the alkaline conditions can be at least about 11.0,11.2, 11.4, 11.6, 11.8, 12.0, 12.2, 12.4, 12.6, 12.8, or 13.0.

Various alkali hydroxides can be used, such as sodium hydroxide,potassium hydroxide, calcium hydroxide, lithium hydroxide, and/ortetraethylammonium hydroxide. The concentration of alkali hydroxide in apreparation with poly alpha-1,3-glucan and a solvent can be from about1-70 wt %, 5-50 wt %, 10-50 wt %, 10-40 wt %, or 10-30 wt % (or anyinteger between 1 and 70 wt %). Alternatively, the concentration ofalkali hydroxide such as sodium hydroxide can be at least about 1, 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22,23, 24, 25, 26, 27, 28, 29, or 30 wt %. An alkali hydroxide used toprepare alkaline conditions may be in a completely aqueous solution oran aqueous solution comprising one or more water-soluble organicsolvents such as ethanol or isopropanol. Alternatively, an alkalihydroxide can be added as a solid to provide alkaline conditions.

Various organic solvents that can optionally be included when preparingthe reaction include alcohols, acetone, dioxane, isopropanol andtoluene, for example; none of these solvents dissolve polyalpha-1,3-glucan. Toluene or isopropanol can be used in certainembodiments. An organic solvent can be added before or after addition ofalkali hydroxide. The concentration of an organic solvent (e.g.,isopropanol or toluene) in a preparation comprising polyalpha-1,3-glucan and an alkali hydroxide can be at least about 10, 15,20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 wt % (orany integer between 10 and 90 wt %).

Alternatively, solvents that can dissolve poly alpha-1,3-glucan can beused when preparing the reaction. These solvents include, but are notlimited to, lithium chloride (LiCl)/N,N-dimethyl-acetamide (DMAc),SO₂/diethylamine (DEA)/climethyl sulfoxide (DMSO),LiCl/1,3-dimethy-2-imidazolidinone (DMI), N,N-dimethylformamide(DMF)/N₂O₄, DMSO/tetrabutyl-ammonium fluoride trihydrate (TBAF),N-methylmorpholine-N-oxide (NMMO), Ni(tren)(OH)₂[tren¼tris(2-aminoethyl)amine] aqueous solutions and melts of LiClO₄.3H₂O, NaOH/urea aqueous solutions, aqueous sodium hydroxide, aqueouspotassium hydroxide, formic acid, and ionic liquids.

Poly alpha-1,3-glucan can be contacted with a solvent and one or morealkali hydroxides by mixing. Such mixing can be performed during orafter adding these components with each other. Mixing can be performedby manual mixing, mixing using an overhead mixer, using a magnetic stirbar, or shaking, for example. In certain embodiments, polyalpha-1,3-glucan can first be mixed in water or an aqueous solutionbefore it is mixed with a solvent and/or alkali hydroxide.

After contacting poly alpha-1,3-glucan, solvent, and one or more alkalihydroxides with each other, the resulting composition can optionally bemaintained at ambient temperature for up to 14 days. The term “ambienttemperature” as used herein refers to a temperature between about 15-30°C. or 20-25° C. (or any integer between 15 and 30° C.). Alternatively,the composition can be heated with or without reflux at a temperaturefrom about 30° C. to about 150° C. (or any integer between 30 and 150°C.) for up to about 48 hours. The composition in certain embodiments canbe heated at about 55° C. for about 30 minutes or 60 minutes. Thus, acomposition obtained from mixing a poly alpha-1,3-glucan, solvent, andone or more alkali hydroxides with each other can be heated at about 50,51, 52, 53, 54, 55, 56, 57, 58, 59, or 60° C. for about 30-90 minutes.

After contacting poly alpha-1,3-glucan, solvent, and one or more alkalihydroxides with each other, the resulting composition can optionally befiltered (with or without applying a temperature treatment step). Suchfiltration can be performed using a funnel, centrifuge, press filter, orany other method and/or equipment known in the art that allows removalof liquids from solids. Though filtration would remove much of thealkali hydroxide, the filtered poly alpha-1,3-glucan would remainalkaline (i.e., mercerized poly alpha-1,3-glucan), thereby providingalkaline conditions.

An etherification agent comprising an organic group can be contactedwith poly alpha-1,3-glucan in a reaction under alkaline conditions in amethod herein of producing poly alpha-1,3-glucan ether compounds. Forexample, an etherification agent can be added to a composition preparedby contacting poly alpha-1,3-glucan, solvent, and one or more alkalihydroxides with each other as described above. Alternatively, anetherification agent can be included when preparing the alkalineconditions (e.g., an etherification agent can be mixed with polyalpha-1,3-glucan and solvent before mixing with alkali hydroxide).

An etherification agent herein refers to an agent that can be used toetherify one or more hydroxyl groups of the glucose units of polyalpha-1,3-glucan with an organic group as defined above. Examples ofsuch organic groups include alkyl groups, hydroxy alkyl groups, andcarboxy alkyl groups. One or more etherification agents may be used inthe reaction.

Etherification agents suitable for preparing an alkyl polyalpha-1,3-glucan ether compound include, for example, dialkyl sulfates,dialkyl carbonates, alkyl halides (e.g., alkyl chloride), iodoalkanes,alkyl triflates (alkyl trifluoromethanesulfonates) and alkylfluorosulfonates. Thus, examples of etherification agents for producingmethyl poly alpha-1,3-glucan ethers include dimethyl sulfate, dimethylcarbonate, methyl chloride, iodomethane, methyl triflate and methylfluorosulfonate. Examples of etherification agents for producing ethylpoly alpha-1,3-glucan ethers include diethyl sulfate, diethyl carbonate,ethyl chloride, iodoethane, ethyl triflate and ethyl fluorosulfonate.Examples of etherification agents for producing propyl polyalpha-1,3-glucan ethers include dipropyl sulfate, dipropyl carbonate,propyl chloride, iodopropane, propyl triflate and propylfluorosulfonate. Examples of etherification agents for producing butylpoly alpha-1,3-glucan ethers include dibutyl sulfate, dibutyl carbonate,butyl chloride, iodobutane and butyl triflate.

Etherification agents suitable for preparing a hydroxyalkyl polyalpha-1,3-glucan ether compound include, for example, alkylene oxidessuch as ethylene oxide, propylene oxide (e.g., 1,2-propylene oxide),butylene oxide (e.g., 1,2-butylene oxide; 2,3-butylene oxide;1,4-butylene oxide), or combinations thereof. As examples, propyleneoxide can be used as an etherification agent for preparing hydroxypropylpoly alpha-1,3-glucan, and ethylene oxide can be used as anetherification agent for preparing hydroxyethyl poly alpha-1,3-glucan.Alternatively, hydroxyalkyl halides (e.g., hydroxyalkyl chloride) can beused as etherification agents for preparing hydroxyalkyl polyalpha-1,3-glucan. Examples of hydroxyalkyl halides include hydroxyethylhalide, hydroxypropyl halide (e.g., 2-hydroxypropyl chloride,3-hydroxypropyl chloride) and hydroxybutyl halide. Alternatively,alkylene chlorohydrins can be used as etherification agents forpreparing hydroxyalkyl poly alpha-1,3-glucan. Alkylene chlorohydrinsthat can be used include, but are not limited to, ethylene chlorohydrin,propylene chlorohydrin, butylene chlorohydrin, or combinations of these.

Etherification agents suitable for preparing a dihydroxyalkyl polyalpha-1,3-glucan ether compound include dihydroxyalkyl halides (e.g.,dihydroxyalkyl chloride) such as dihydroxyethyl halide, dihydroxypropylhalide (e.g., 2,3-dihydroxypropyl chloride [i.e.,3-chloro-1,2-propanediol]), or dihydroxybutyl halide, for example.2,3-dihydroxypropyl chloride can be used to prepare dihydroxypropyl polyalpha-1,3-glucan, for example.

Etherification agents suitable for preparing a carboxyalkyl polyalpha-1,3-glucan ether compound may include haloalkylates (e.g.,chloroalkylate). Examples of haloalkylates include haloacetate (e.g.,chloroacetate), 3-halopropionate (e.g., 3-chloropropionate) and4-halobutyrate (e.g., 4-chlorobutyrate). For example, chloroacetate(monochloroacetate) (e.g., sodium chloroacetate or chloroacetic acid)can be used as an etherification agent to prepare carboxymethyl polyalpha-1,3-glucan.

When producing a poly alpha-1,3-glucan ether compound with two or moredifferent organic groups, two or more different etherification agentswould be used, accordingly. For example, both an alkylene oxide and analkyl chloride could be used as etherification agents to produce analkyl hydroxyalkyl poly alpha-1,3-glucan ether. Any of theetherification agents disclosed herein may therefore be combined toproduce poly alpha-1,3-glucan ether compounds with two or more differentorganic groups. Such two or more etherification agents may be used inthe reaction at the same time, or may be used sequentially in thereaction. When used sequentially, any of the temperature-treatment(e.g., heating) steps disclosed below may optionally be used betweeneach addition. One may choose sequential introduction of etherificationagents in order to control the desired DoS of each organic group. Ingeneral, a particular etherification agent would be used first if theorganic group it forms in the ether product is desired at a higher DoScompared to the DoS of another organic group to be added.

The amount of etherification agent to be contacted with polyalpha-1,3-glucan in a reaction under alkaline conditions can bedetermined based on the degree of substitution required in the polyalpha-1,3-glucan ether compound being produced. The amount of ethersubstitution groups on each monomeric unit in poly alpha-1,3-glucanether compounds produced herein can be determined using nuclear magneticresonance (NMR) spectroscopy. The molar substitution (MS) value for polyalpha-1,3-glucan has no upper limit. In general, an etherification agentcan be used in a quantity of at least about 0.05 mole per mole of polyalpha-1,3-glucan. There is no upper limit to the quantity ofetherification agent that can be used.

Reactions for producing poly alpha-1,3-glucan ether compounds herein canoptionally be carried out in a pressure vessel such as a Parr reactor,an autoclave, a shaker tube or any other pressure vessel well known inthe art. A shaker tube is used to perform the reaction in certainembodiments.

A reaction herein can optionally be heated following the step ofcontacting poly alpha-1,3-glucan with an etherification agent underalkaline conditions. The reaction temperatures and time of applying suchtemperatures can be varied within wide limits. For example, a reactioncan optionally be maintained at ambient temperature for up to 14 days.Alternatively, a reaction can be heated, with or without reflux, betweenabout 25° C. to about 200° C. (or any integer between 25 and 200° C.).Reaction time can be varied correspondingly: more time at a lowtemperature and less time at a high temperature.

Optionally, a reaction herein can be maintained under an inert gas, withor without heating. As used herein, the term “inert gas” refers to a gaswhich does not undergo chemical reactions under a set of givenconditions, such as those disclosed for preparing a reaction herein.

All of the components of the reactions disclosed herein can be mixedtogether at the same time and brought to the desired reactiontemperature, whereupon the temperature is maintained with or withoutstirring until the desired poly alpha-1,3-glucan ether compound isformed. Alternatively, the mixed components can be left at ambienttemperature as described above.

Following etherification, the pH of a reaction can be neutralized.Neutralization of a reaction can be performed using one or more acids.The term “neutral pH” as used herein, refers to a pH that is neithersubstantially acidic or basic (e.g., a pH of about 6-8, or about 6.0,6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, or 8.0). Various acids thatcan be used for this purpose include, but are not limited to, sulfuric,acetic, hydrochloric, nitric, any mineral (inorganic) acid, any organicacid, or any combination of these acids.

A poly alpha-1,3-glucan ether compound produced in a reaction herein canoptionally be washed one or more times with a liquid that does notreadily dissolve the compound. For example, poly alpha-1,3-glucan ethercan be washed with water, alcohol, acetone, aromatics, or anycombination of these, depending on the solubility of the ether compoundtherein (where lack of solubility is desirable for washing). In general,a solvent comprising an organic solvent such as alcohol is preferred forwashing a poly alpha-1,3-glucan ether. A poly alpha-1,3-glucan etherproduct can be washed one or more times with an aqueous solutioncontaining methanol or ethanol, for example. For example, 70-95 wt %ethanol can be used to wash the product. A poly alpha-1,3-glucan etherproduct can be washed with a methanol:acetone (e.g., 60:40) solution inanother embodiment. Hot water (about 95-100° C.) can be used in certainembodiments, such as for washing alkyl poly alpha-1,3-glucan ethers(e.g., ethyl poly alpha-1,3-glucan) and alkyl hydroxyalkyl polyalpha-1,3-glucan ethers (e.g., ethyl hydroxyethyl polyalpha-1,3-glucan).

A poly alpha-1,3-glucan ether produced in the disclosed reaction can beisolated. This step can be performed before or after neutralizationand/or washing steps using a funnel, centrifuge, press filter, or anyother method or equipment known in the art that allows removal ofliquids from solids. For example, a Buchner funnel may be used toisolate a poly alpha-1,3-glucan ether product. An isolated polyalpha-1,3-glucan ether product can be dried using any method known inthe art, such as vacuum drying, air drying, or freeze drying.

Any of the above etherification reactions can be repeated using a polyalpha-1,3-glucan ether product as the starting material for furthermodification. This approach may be suitable for increasing the DoS of anorganic group, and/or adding one or more different organic groups to theether product.

The structure, molecular weight and degree of substitution of a polyalpha-1,3-glucan ether product can be confirmed using variousphysiochemical analyses known in the art such as NMR spectroscopy andsize exclusion chromatography (SEC).

The percentage of glycosidic linkages between the glucose monomer unitsof poly alpha-1,3-glucan used to prepare poly alpha-1,3-glucan ethercompounds herein that are alpha-1,3 is at least about 50%, 60%, 70%,80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% (or any integer value between50% and 100%). In such embodiments, accordingly, poly alpha-1,3-glucanhas less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1%, or 0%(or any integer value between 0% and 50%) of glycosidic linkages thatare not alpha-1,3.

Poly alpha-1,3-glucan used to prepare poly alpha-1,3-glucan ethercompounds herein is preferably linear/unbranched. In certainembodiments, poly alpha-1,3-glucan has no branch points or less thanabout 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% branch points as apercent of the glycosidic linkages in the polymer. Examples of branchpoints include alpha-1,6 branch points.

The M_(n) or M_(w) of poly alpha-1,3-glucan used to prepare polyalpha-1,3-glucan ether compounds herein may be at least about 1000 toabout 600000. Alternatively still, M_(n) or M_(w) can be at least about2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000,25000, 30000, 35000, 40000, 45000, 50000, 75000, 100000, 150000, 200000,250000, 300000, 350000, 400000, 450000, 500000, 550000, or 600000 (orany integer between 2000 and 600000), for example.

Poly alpha-1,3-glucan used for preparing poly alpha-1,3-glucan ethercompounds herein can be enzymatically produced from sucrose using one ormore glucosyltransferase (gtf) enzymes. The poly alpha-1,3-glucanproduct of this enzymatic reaction can be purified before using it toprepare an ether using the disclosed process. Alternatively, a polyalpha-1,3-glucan product of a gtf reaction can be used with little or noprocessing for preparing poly alpha-1,3-glucan ether compounds.

A poly alpha-1,3-glucan slurry can be used directly in any of the aboveprocesses for producing a poly alpha-1,3-glucan ether compound disclosedherein. As used herein, a “poly alpha-1,3-glucan slurry” refers to amixture comprising the components of a gtf enzymatic reaction. A gtfenzymatic reaction can include, in addition to poly alpha-1,3-glucanitself, various components such as sucrose, one or more gtf enzymes,glucose, fructose, leucrose, buffer, FermaSure®, solubleoligosaccharides, oligosaccharide primers, bacterial enzyme extractcomponents, borates, sodium hydroxide, hydrochloric acid, cell lysate,proteins and/or nucleic acids. Minimally, the components of a gtfenzymatic reaction can include, in addition to poly alpha-1,3-glucanitself, sucrose, one or more gtf enzymes, glucose, and fructose, forexample. In another example, the components of a gtf enzymatic reactioncan include, in addition to poly alpha-1,3-glucan itself, sucrose, oneor more gtf enzymes, glucose, fructose, leucrose and solubleoligosaccharides (and optionally bacterial enzyme extract components).It should be apparent that poly alpha-1,3-glucan, when in a slurry asdisclosed herein, has not been purified or washed. It should also beapparent that a slurry represents a gtf enzymatic reaction that iscomplete or for which an observable amount of poly alpha-1,3-glucan hasbeen produced, which forms a solid since it is insoluble in the aqueousreaction milieu (has pH of 5-7, for example). A poly alpha-1,3-glucanslurry can be prepared by setting up a gtf reaction as disclosed in U.S.Pat. No. 7,000,000 or U.S. Patent Appl. Publ. Nos. 2013/0244288 and2013/0244287, for example, all of which are incorporated herein byreference. A poly alpha-1,3-glucan slurry can be entered, for example,into a reaction for producing a carboxyalkyl poly alpha-1,3-glucan suchas carboxymethyl poly alpha-1,3-glucan. Some embodiments herein aredrawn to compositions comprising poly alpha-1,3-glucan ether and aglucosyltransferase enzyme (e.g., such a composition may result whenusing a slurry in an etherification reaction herein).

Alternatively, a wet cake of poly alpha-1,3-glucan can be used directlyin any of the above processes for producing a poly alpha-1,3-glucanether compound disclosed herein. A “wet cake of poly alpha-1,3-glucan”as used herein refers to poly alpha-1,3-glucan that has been separated(e.g., filtered) from a slurry and washed with water or an aqueoussolution. A wet cake can be washed at least 1, 2, 3, 4, 5, or moretimes, for example. The poly alpha-1,3-glucan is not dried whenpreparing a wet cake. A wet cake is termed as “wet” given the retentionof water by the washed poly alpha-1,3-glucan.

A wet cake of poly alpha-1,3-glucan can be prepared using any deviceknown in the art for separating solids from liquids, such as a filter orcentrifuge. For example, poly alpha-1,3-glucan solids in a slurry can becollected on a Buchner funnel using a mesh screen over filter paper.Filtered wet cake can be resuspended in water (e.g., deionized water)and filtered one or more times to remove soluble components of theslurry such as sucrose, fructose and leucrose. As another example forpreparing a wet cake, poly alpha-1,3-glucan solids from a slurry can becollected as a pellet via centrifugation, resuspended in water (e.g.,deionized water), and re-pelleted and resuspended one or more additionaltimes. A poly alpha-1,3-glucan wet cake can be entered into a reactionfor producing any ether compound herein, such as carboxyalkyl polyalpha-1,3-glucan (e.g., carboxymethyl poly alpha-1,3-glucan).

Poly alpha-1,3-glucan ether compounds disclosed herein may becrosslinked using any means known in the art. Such crosslinkage may bebetween the same poly alpha-1,3-glucan ether compounds, or between twoor more different poly alpha-1,3-glucan ether compounds. Also,crosslinkage may be intermolecular and/or intramolecular.

A crosslinked poly alpha-1,3-glucan ether compound can be prepared asfollows, for example. One or more poly alpha-1,3-glucan ether compoundscan be dissolved in water or an aqueous solution to prepare a 0.2, 0.5,1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt % solution of the ether compound(s).Poly alpha-1,3-glucan ether compound(s) can be dissolved or mixed usingany process known in the art, such as by increasing temperature, manualmixing, and/or homogenization (as described above).

A crosslinking agent is next dissolved in the poly alpha-1,3-glucanether solution or mixture. The concentration of the crosslinking agentin the resulting solution can be about 0.2 to 20 wt %, or about 0.1,0.2, 0.3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt %.

Examples of suitable crosslinking agents are boron-containing compoundsand polyvalent metals such as titanium or zirconium. Boron-containingcompounds include boric acid, diborates, tetraborates, pentaborates,polymeric compounds such as Polybor®, polymeric compounds of boric acid,and alkali borates, for example. These agents can be used to produceborate crosslinks between poly alpha-1,3-glucan ether molecules.Titanium crosslinks may be produced using titanium IV-containingcompounds (e.g., titanium ammonium lactate, titanium triethanolamine,titanium acetylacetonate, polyhydroxy complexes of titanium) ascrosslinking agents. Zirconium crosslinks can be produced usingzirconium IV-containing compounds (e.g., zirconium lactate, zirconiumcarbonate, zirconium acetylacetonate, zirconium triethanolamine,zirconium diisopropylamine lactate, polyhydroxy complexes of zirconium)as crosslinking agents. Other examples of crosslinking agents usefulherein are described in U.S. Pat. Nos. 4,462,917, 4,464,270, 4,477,360and 4,799,550, which are all incorporated herein by reference.

The pH of the solution or mixture containing both a crosslinkingagent(s) and a poly alpha-1,3-glucan ether compound(s) can be adjustedto be alkali (e.g., pH of 8, 8.5, 9, 9.5, or 10). Modification of pH canbe done by any means known in the art, such as with a concentratedaqueous solution of an alkali hydroxide such as sodium hydroxide.Dissolving a crosslinking agent in a solution or mixture containing oneor more poly alpha-1,3-glucan ether compounds at an alkali pH results incrosslinking of the poly alpha-1,3-glucan ether compound(s).

Non-limiting examples of compositions and methods disclosed hereininclude:

-   1. A composition comprising a cellulase and a poly alpha-1,3-glucan    ether compound represented by the structure:

-   -   wherein    -   (i) n is at least 6,    -   (ii) each R is independently an H or an organic group, and    -   (iii) the compound has a degree of substitution of about 0.05 to        about 3.0.

-   2. The composition of embodiment 1, wherein at least one organic    group is selected from the group consisting of carboxy alkyl group,    hydroxy alkyl group, and alkyl group.

-   3. The composition of embodiment 2, wherein at least one organic    group is selected from the group consisting of carboxymethyl,    hydroxypropyl, dihydroxypropyl, hydroxyethyl, methyl, and ethyl    group.

-   4. The composition of embodiment 2, wherein the organic group is a    carboxymethyl group.

-   5. The composition of embodiment 1, 2, 3, or 4, wherein the    composition is in the form of a personal care product, household    product, or industrial product.

-   6. The composition of embodiment 5, wherein the composition is a    fabric care product.

-   7. The composition of embodiment 1, 2, 3, 4, 5, or 6, wherein the    composition is an aqueous composition.

-   8. The composition of embodiment 7, wherein the composition has a    viscosity of at least about 10 cPs.

-   9. A method for preparing an aqueous composition, the method    comprising: contacting an aqueous composition with a poly    alpha-1,3-glucan ether compound represented by the structure:

-   -   wherein    -   (i) n is at least 6,    -   (ii) each R is independently an H or an organic group, and    -   (iii) the compound has a degree of substitution of about 0.05 to        about 3.0;    -   and wherein the aqueous composition prepared in the method        comprises a cellulase.

-   10. The method of embodiment 9, wherein the cellulase is:    -   (i) comprised in the aqueous composition prior to the contacting        step, or    -   (ii) added to the aqueous composition during or after the        contacting step.

-   11. The method of embodiment 9 or 10, wherein:    -   (i) the viscosity of the aqueous composition is increased by the        poly alpha-1,3-glucan ether compound, and/or    -   (ii) the shear thinning behavior or the shear thickening        behavior of the aqueous composition is increased by the poly        alpha-1,3-glucan ether compound.

-   12. A method of treating a material, the method comprising:    -   contacting a material with an aqueous composition comprising a        cellulase and a poly alpha-1,3-glucan ether compound represented        by the structure:

-   -   wherein    -   (i) n is at least 6,    -   (ii) each R is independently an H or an organic group, and    -   (iii) the compound has a degree of substitution of about 0.05 to        about 3.0.

-   13. The method of embodiment 12, wherein the material comprises    fabric.

-   14. The method of embodiment 13 wherein the fabric comprises a (i)    natural fiber, (ii) synthetic fiber, or a combination of both (i)    and (ii).

-   15. The method of embodiment 13 or 14, wherein the poly    alpha-1,3-glucan ether compound adsorbs to the fabric.

Examples

The present disclosure is further exemplified in the following Examples.It should be understood that these Examples, while indicating certainpreferred aspects herein, are given by way of illustration only. Fromthe above discussion and these Examples, one skilled in the art canascertain the essential characteristics of the disclosed embodiments,and without departing from the spirit and scope thereof, can makevarious changes and modifications to adapt the disclosed embodiments tovarious uses and conditions.

Abbreviations

The meaning of some of the abbreviations used herein is as follows: “g”means gram(s), “h” means hour(s), “mL” means milliliter(s), “psi” meanspound(s) per square inch, “wt %” means weight percentage, “μm” meansmicrometer(s), “° C.” means degrees Celsius, “mg” means milligram(s),“mm” means millimeter(s), “m” means meter(s), “μL” means microliter(s),“mmol” means millimole(s), “min” means minute(s), “mol %” means molepercent, “M” means molar, “rpm” means revolutions per minute, “MPa”means megaPascals, “CMG” means carboxymethyl glucan, and “CMC” meanscarboxymethyl cellulose.

General Methods

All reagents were obtained from Sigma-Aldrich (St. Louis, Mo.) unlessstated otherwise. Carboxymethyl cellulose ether derivative (CMC,Sigma-Aldrich product no. 419273) had a M_(w) of about 90000 and adegree of substitution (DoS) of 0.7 carboxymethyl groups per glucoseunit. PREFERENZ S100 amylase, PURASTAR ST L amylase, PURADAX HA1200Ecellulase and PURADAX EG L cellulase were from DuPont IndustrialBiosciences.

Preparation of Poly Alpha-1,3-Glucan

Poly alpha-1,3-glucan was prepared using a gtfJ enzyme preparation asdescribed in U.S. Patent Appl. Publ. No. 2013/0244288, which isincorporated herein by reference in its entirety.

Preparation of Sodium Carboxymethyl Poly Alpha-1,3-Glucan

10 g of poly alpha-1,3-glucan (M_(w) [weight-average molecularweight]=236,854) was added to 200 mL of isopropanol in a 500-mL capacityround bottom flask fitted with a thermocouple for temperature monitoringand a condenser connected to a recirculating bath, and a magnetic stirbar. 40 mL of sodium hydroxide (15% solution) was added dropwise to thepreparation, which was then heated to 25° C. on a hotplate. Thepreparation was stirred for 1 hour before the temperature was increasedto 55° C. Sodium chloroacetate (12 g) was then added to provide areaction, which was held at 55° C. for 3 hours before being neutralizedwith 90% acetic acid. The solid thus formed was collected by vacuumfiltration and washed with ethanol (70%) four times, dried under vacuumat 20-25° C., and analyzed by NMR and SEC to determine molecular weightand DoS. The solid material obtained was identified as water-solublesodium carboxymethyl poly alpha-1,3-glucan with a DoS of 0.5 and anM_(w) of 580,000.

Table 1 provides a list of DoS measurements for various samples ofcarboxymethyl poly alpha-1,3-glucan prepared using the above method. Thepoly alpha-1,3-glucan starting material had various molecular weights(Table 1).

TABLE 1 DoS of Carboxymethyl Poly Alpha-1,3-Glucan Prepared from PolyAlpha-1,3-Glucan M_(w) of poly CMG alpha-1,3- Sample glucan startingDesignation material DoS 1A (35) 140287 0.5 1B (36) 140287 0.9 1C (39)140287 1 1D (44) 88445 0.7 1E (47) 278858 0.7 1F (58) 248006 1G (67)236854 0.5 1H (72) 236854 0.9 1I (−41) 200000 0.5 1J (−39) 168584 0.5D102709-44 98133 0.47

Preparation of Potassium/Sodium Carboxymethyl Poly Alpha-1,3-Glucan

10 g of poly alpha-1,3-glucan (M_(w)=168,000) was added to 200 mL ofisopropanol in a 500-mL capacity round bottom flask fitted with athermocouple for temperature monitoring and a condenser connected to arecirculating bath, and a magnetic stir bar. 40 mL of potassiumhydroxide (15% solution) was added dropwise to this preparation, whichwas then heated to 25° C. on a hotplate. The preparation was stirred for1 hour before the temperature was increased to 55° C. Sodiumchloroacetate (12 g) was then added to provide a reaction, which washeld at 55° C. for 3 hours before being neutralized with 90% aceticacid. The solid thus formed was collected by vacuum filtration andwashed with ethanol (70%) four times, dried under vacuum at 20-25° C.,and analyzed by NMR and SEC to determine molecular weight and DoS. Thesolid material obtained was identified as water soluble potassium/sodiumcarboxymethyl poly alpha-1,3-glucan with a DoS of 0.77. This procedurecould be adapted to produce potassium carboxymethyl polyalpha-1,3-glucan by simply using chloroacetic acid, instead of sodiumchloroacetate, as the etherification agent.

Preparation of Lithium/Sodium Carboxymethyl Poly Alpha-1,3-Glucan

10 g of poly alpha-1,3-glucan (M_(w)=168,000) was added to 200 mL ofisopropanol in a 500-mL capacity round bottom flask fitted with athermocouple for temperature monitoring and a condenser connected to arecirculating bath, and a magnetic stir bar. 50 mL of lithium hydroxide(11.3% solution) was added dropwise to this preparation, which was thenheated to 25° C. on a hotplate. The preparation was stirred for 1 hourbefore the temperature was increased to 55° C. Sodium chloroacetate (12g) was then added to provide a reaction, which was held at 55° C. for 3hours before being neutralized with 90% acetic acid. The solid thusformed was collected by vacuum filtration and washed with ethanol (70%)four times, dried under vacuum at 20-25° C., and analyzed by NMR and SECto determine molecular weight and DoS. The solid material obtained wasidentified as water soluble CMG with a DoS of 0.79 (sample 2A). Reagentamounts were adjusted to prepare another CMG sample, which had a DoS of0.36 (sample 2B). This procedure could be adapted to produce lithiumcarboxymethyl poly alpha-1,3-glucan by simply using chloroacetic acid,instead of sodium chloroacetate, as the etherification agent.

Preparation of Carboxymethyl Poly Alpha-1,3-Glucan from PolyAlpha-1,3-Glucan Slurry

Poly alpha-1,3-glucan slurry (500 g, see below) was placed in a 1-Ljacketed reaction vessel fitted with a thermocouple for temperaturemonitoring, a condenser connected to a recirculating bath, and amagnetic stir bar. Solid sodium hydroxide (75 g) was added to the slurryto yield a preparation with 15 wt % sodium hydroxide. This preparationwas heated to 25° C. on a hotplate. The preparation was then stirred for1 hour before the temperature was increased to 55° C. Sodiumchloroacetate (227.3 g) was added to the preparation and the reactiontemperature was held at 55° C. for 3 hours. The reaction was thenneutralized with acetic acid (90%). The solid was collected by vacuumfiltration and washed with ethanol (70%) four times, dried under vacuumat 20-25° C., and analyzed by NMR and SEC to determine molecular weightand DoS. The solid material obtained was identified as water-solublecarboxymethyl poly alpha-1,3-glucan with a DoS of 0.3 and a M_(w) of140,000.

Preparation of Carboxymethyl Poly Alpha-1,3-Glucan from PolyAlpha-1,3-Glucan Wet Cake

Poly alpha-1,3-glucan wet cake (500 g, see below) was placed in a 1-Ljacketed reaction vessel fitted with a thermocouple for temperaturemonitoring, a condenser connected to a recirculating bath, and anoverhead stirrer. Isopropanol (500 mL) and solid sodium hydroxide (79.1g) were added to the wet cake to yield a preparation with 15 wt % sodiumhydroxide. This preparation was heated to 25° C. on a hotplate, and thenstirred for 1 hour before the temperature was increased to 55° C. Sodiumchloroacetate (227.3 g) was added to the preparation and the reactiontemperature was held at 55° C. for 3 hours. The reaction was thenneutralized with acetic acid (90%). The solids were collected by vacuumfiltration and washed with ethanol (70%) four times, dried under vacuumat 20-25° C., and analyzed by NMR and SEC to determine molecular weightand DoS. The solid material obtained was identified as water-solublecarboxymethyl poly alpha-1,3-glucan with a DoS of 0.7 and a M_(w) of250,000.

Preparation of Hydroxypropyl Poly Alpha-1,3-Glucan (HPG)

10 g of poly alpha-1,3-glucan (number-average molecular weight[M_(e)]=71127) was mixed with 101 g of toluene and 5 mL of 20% sodiumhydroxide. This preparation was stirred in a 500-mL glass beaker on amagnetic stir plate at 55° C. for 30 minutes. The preparation was thentransferred to a shaker tube reactor after which 34 g of propylene oxidewas added; the reaction was then stirred at 75° C. for 3 hours. Thereaction was then neutralized with 20 g of acetic acid and thehydroxypropyl poly alpha-1,3-glucan solids thus formed were filteredwith a Buchner funnel. The solids were then washed in a beaker with 70%ethanol and dried in a vacuum oven with a slight nitrogen bleed untilconstant dryness was achieved. The molar substitution (MS) of the driedproduct was reported by NMR to be 3.89 (sample 1).

An additional sample of HPG was produced following another method. 10 gof poly alpha-1,3-glucan (M_(w)=168584) was added to 101 mL of tolueneand 5 mL of 20 wt % sodium hydroxide in a 400-mL beaker with a magneticstir bar. The beaker was stirred on a magnetic stir plate at 375 rpm forone hour at 55° C. This preparation was then placed in a 200-mL capacityjar with a lid and allowed to sit overnight before being transferred toa 250-mL capacity shaker tube reactor. The reactor was heated to 75° C.and charged with 34 g of 1,2-propylene oxide. The reaction was held attemperature for 4 hours. After cooling, the reaction was neutralizedwith 90% acetic acid. The solid was collected by vacuum filtration,washed with hot water three times, dried under vacuum at 20-25° C., andanalyzed by NMR to determine DoS. The solid material was determined tobe HPG (sample 2).

Preparation of a Dihydroxypropyl Poly Alpha-1,3-Glucan

10 g of poly alpha-1,3-glucan (M_(w)=138,438) was added to 100 mL of 20%tetraethylammonium hydroxide in a 500-mL capacity round bottom flaskfitted with a thermocouple for temperature monitoring and a condenserconnected to a recirculating bath, and a magnetic stir bar (resulting in˜9.1 wt % poly alpha-1,3-glucan). This preparation was stirred andheated to 30° C. on a hotplate. The preparation was stirred for 1 hourto dissolve the solid before the temperature was increased to 55° C.3-chloro-1,2-propanediol (6.7 g) and 11 g of DI water were then added toprovide a reaction (containing ˜5.2 wt % 3-chloro-1,2-propanediol),which was held at 55° C. for 1.5 hours afterwhich time 5.6 g of DI waterwas added to the reaction. The reaction was held at 55° C. for anadditional 3 hours and 45 minutes before being neutralized with aceticacid. After neutralization, an excess of isopropanol was added toprecipitate a solid. The solid thus formed was collected by vacuumfiltration and washed with ethanol (95%) four times, and dried undervacuum at 20-25° C. The solid material obtained was identified asdihydroxypropyl poly alpha-1,3-glucan that was not water soluble, andhaving a degree of substitution of 0.6.

The above procedure was repeated with some modification, and this timeusing a sample of the dihydroxypropyl poly alpha-1,3-glucan preparedabove as the starting material. Briefly, 5 g of the glucan ether wasadded to 50 mL of 20% tetraethylammonium hydroxide. This preparation wasstirred with a magnetic stir bar until the solid dissolved, and thenheated to 30° C. for 1 hour on a hotplate. The preparation was thenheated to 55° C. and 3-chloro-1,2-propanediol (8 g) was added to providea reaction. The reaction was then stirred for 2 hours, afterwhich timeit was neutralized with acetic acid. After neutralization, an excess ofisopropanol was added to precipitate a solid. The solid thus formed wascollected by vacuum filtration and washed with ethanol (95%) four times,and dried under vacuum at 20-25° C. The solid material obtained wasidentified as dihydroxypropyl poly alpha-1,3-glucan that was watersoluble, and having a degree of substitution of 0.89 (sample 1).

An additional sample of dihydroxypropyl poly alpha-1,3-glucan wasproduced following another method. 10 g of poly alpha-1,3-glucan(M_(w)=138,438) was added to 143 g of 20% tetraethylammonium hydroxidein a 500-mL capacity round bottom flask fitted with a thermocouple fortemperature monitoring and a condenser connected to a recirculatingbath, and a magnetic stir bar (resulting in ˜6.5 wt % polyalpha-1,3-glucan). This preparation was stirred and heated to 30° C. ona hotplate. The preparation was stirred for 1 hour to dissolve the solidbefore the temperature was increased to 55° C. 3-chloro-1,2-propanediol(16 g) was then added to provide a reaction (containing ˜9.5 wt %3-chloro-1,2-propanediol), which was held at 55° C. for 2 hours beforebeing neutralized with acetic acid. After neutralization, an excess ofisopropanol was added to precipitate a solid. The solid thus formed wascollected by vacuum filtration and washed with ethanol (95%) four times,and dried under vacuum at 20-25° C. The solid material obtained wasidentified as dihydroxypropyl poly alpha-1,3-glucan that was watersoluble, and having a degree of substitution of 0.6 (sample 2).

Preparation of Hydroxyethyl Poly Alpha-1,3-Glucan

10 g of poly alpha-1,3-glucan (M_(n)=71127) was mixed with 150 mL ofisopropanol and 40 mL of 30% sodium hydroxide. This preparation wasstirred in a 500-mL glass beaker on a magnetic stir plate at 55° C. for1 hour, and then stirred overnight at ambient temperature. Thepreparation was then transferred to a shaker tube reactor after which 15g of ethylene oxide was added; the reaction was then stirred at 60° C.for 6 hour. The reaction was then allowed to remain in the sealed shakertube overnight (approximately 16 hours) before it was neutralized with20.2 g of acetic acid thereby forming hydroxyethyl poly alpha-1,3-glucansolids. The solids were filtered using a Buchner funnel with35-micrometer filter paper. The solids were then washed in a beaker byadding a methanol:acetone (60:40 v/v) mixture and stirring with a stirbar for 20 minutes. The methanol:acetone mixture was then filtered awayfrom the solids. This washing step was repeated two times. The solids,which had a slightly brown/beige color, were dried in a vacuum oven witha nitrogen bleed. The hydroxyethyl poly alpha-1,3-glucan product wassoluble in a 10% NaOH solution. The MS of the dried product was reportedby NMR to be 0.72.

Preparation of Methyl Poly Alpha-1,3-Glucan (MG)

10 g of poly alpha-1,3-glucan (M_(n)=71127) was mixed with 40 mL of 30%sodium hydroxide and 40 mL of 2-propanol, and stirred at 55° C. for 1hour to provide alkali poly alpha-1,3-glucan. This preparation was thenfiltered using a Buchner funnel. The alkali poly alpha-1,3-glucan wasthen mixed with 150 mL of 2-propanol to make a slurry. A shaker tubereactor was charged with this slurry and 15 g of methyl chloride wasadded to provide a reaction. The reaction was stirred at 70° C. for 17hours. The resulting methyl poly alpha-1,3-glucan solid was filtered andneutralized with 20 mL 90% acetic acid, followed by three 200-mL ethanolwashes. NMR analysis was performed, indicating that the DoS of themethyl poly alpha-1,3-glucan product was 1.2.

Table 2 provides a list of DoS measurements for various samples ofmethyl poly alpha-1,3-glucan prepared using methods having certainmodifications compared to the above method (refer to Table 2). Themercerization step (alkali treatment of poly alpha-1,3-glucan prior toaddition of methylating reagent) for each of the processes listed inTable 2 was conducted for 1 hour, as above.

TABLE 2 Preparation of Methyl Poly Alpha-1,3-Glucan Using VariousMercerization and Methylation Conditions Mercerization conditionsMethylation conditions Glucan Temp Time Temp M_(n) (° C.) SolventReagent (hours) (° C.) DoS 71127 RT Toluene DMS^(a) 17 50 1.51 (140 mL)(50 mL) 71127 55 2-propanol CH₃Cl 17 70 1.2 (150 mL) (15 g) 71127 552-propanol CH₃Cl 24 70 1.38 (150 mL) (25 g) 25084 55 2-propanol CH₃Cl 3470 1.0 (150 mL) (30 g) 25084 55 2-propanol CH₃Cl 24 70 0.39 (150 mL) (25g) ^(a)Dimethyl sulfate

Additional samples of methyl poly alpha-1,3-glucan (MG) were producedfollowing another method.

Sample 1

10 g of poly alpha-1,3-glucan (M_(w)=168584) was added to 40 mL ofisopropanol and 40 mL of 30 wt % sodium hydroxide in a 400-mL beakerwith a magnetic stir bar. The beaker was stirred on a magnetic stirplate at 375 rpm for one hour. The solid from this preparation was thencollected by vacuum filtration, mixed with 150 mL of isopropanol, andplaced in a 200-mL capacity jar with a lid. This preparation satovernight before being transferred to a 250-mL capacity shaker tubereactor. The reactor was heated to 70° C. and charged with 10 g ofmethyl chloride. The reaction was held at temperature for 17 hours andthen charged with an additional 20 g of methyl chloride and held attemperature for 17 hours. After cooling, the reaction was neutralizedwith 90% acetic acid. The solid from this reaction was collected byvacuum filtration, washed with methanol three times, dried under vacuumat 20-25° C., and analyzed by NMR to determine DoS. The solid materialobtained was identified as MG with a DoS of 1.75.

8 g of this MG was then mixed with 50 mL isopropanol and 32 mL of 30 wt% sodium hydroxide in a 400-mL beaker with a magnetic stir bar. Thebeaker was stirred on a magnetic stir plate at 375 rpm for one hour. Thesolid was then collected by vacuum filtration, mixed with 150 mL ofisopropanol, and placed in a 200-mL capacity jar with a lid. Thispreparation sat overnight before being transferred to a 250-mL capacityshaker tube reactor. The reactor was heated to 70° C. and charged with12 g of methyl chloride. After cooling, the reaction was neutralizedwith 90% acetic acid. The solid was collected by vacuum filtration andwashed with methanol:acetone (60:40) five times, dried under vacuum at20-25° C., and analyzed by NMR to determine DoS. The solid materialobtained was identified as MG with a DoS of 1.8. This MG was denoted asSample 1.

Sample 2

20 g of poly alpha-1,3-glucan (M_(w)=245,000) was added to 50 mL ofisopropanol and 80 mL of 30 wt % sodium hydroxide in a 400-mL beakerwith a magnetic stir bar. The beaker was stirred on a magnetic stirplate at 375 rpm for one hour. The solid from this preparation was thencollected by vacuum filtration, mixed with 150 mL of isopropanol, andplaced in a 200-mL capacity jar with a lid. This preparation satovernight before being transferred to a 250-mL capacity shaker tubereactor. The reactor was heated to 70° C. and charged with 30 g ofmethyl chloride. The reaction was held at temperature for 17 hours.After cooling, the reaction was neutralized with 90% acetic acid. Thesolid from this reaction was collected by vacuum filtration, washed withmethanol:acetone (60:40) five times, dried under vacuum at 20-25° C.,and analyzed by NMR to determine DoS. The solid material obtained wasidentified as MG with a DoS of 1.39.

10 g of this MG was then mixed with 50 mL isopropanol and 40 mL of 30 wt% sodium hydroxide solution in a 400-mL beaker with a magnetic stir bar.The beaker was stirred on a magnetic stir plate at 375 rpm for one hour.The solid from this preparation was then collected by vacuum filtration,mixed with 100 mL of isopropanol, and placed in a 200-mL capacity jarwith a lid. This preparation sat overnight before being transferred to a250-mL capacity shaker tube reactor. The reactor was heated to 70° C.and charged with 15 g of methyl chloride. After cooling, the reactionwas neutralized with 90% acetic acid. The solid was collected by vacuumfiltration and washed with methanol:acetone (60:40) five times, driedunder vacuum at 20-25° C., and analyzed by NMR to determine DoS. Thesolid material obtained was identified as MG. This MG was denoted asSample 2.

Additional samples of methyl poly alpha-1,3-glucan (MG) were producedusing one-pot and two-pot synthesis strategies, as follows.

One-Pot Synthesis:

10 g (0.0617 moles) of poly alpha-1,3-glucan (M_(w)=˜160000) and 25.55 gof 30% sodium hydroxide (total NaOH=7.665 g [0.192 moles]) were chargedto a shaker tube. Then, 70 g (1.386 moles) of methyl chloride was added.This preparation was placed into a sealed pressure vessel, heated to 50°C., and shaken for 10 hours. The solid contents were then isolated. 40.7g of solids was placed into 150 mL of 95° C. water, stirred for 30seconds and filtered (filtrate was yellow). The solids were againstirred in water at 80-90° C. for 3 minutes; the pH of the solids wasdetermined to be neutral. The final solid material was filtered anddried in an 85° C. vacuum oven to afford 7.6 g of a tan solid. Thismaterial was analyzed by NMR, which determined that methyl polyalpha-1,3-glucan was produced having a DoS of about 1.35.

Two-Pot Synthesis:

A 3-neck 250-mL round bottom flask with magnetic stir bar was chargedwith 200 g of 30% sodium hydroxide and 10 g (0.0617 moles) of polyalpha-1,3-glucan (M_(w)=˜160000). This preparation was stirred at roomtemperature for 60 minutes. The solid was then filtered and airswept-dried in the filter for 5 minutes to yield 35.547 g of off-whitesolids. The solids were then charged into a pressure vessel along with100 g of methyl chloride and the contents were stirred at 50° C. for 10hours. The solids were collected and placed into 150 mL of 95° C. water,stirred for 30 seconds, and filtered (filtrate was yellow). The solidswere again stirred in water at 80-90° C. for 3 minutes; the pH of thesolids was determined to be neutral. The final solid material wasfiltered and dried in an 85° C. vacuum oven to afford 7.3 g of anoff-white solid. This material was analyzed by NMR, which determinedthat methyl poly alpha-1,3-glucan was produced having a DoS of about1.41.

Viscosity Analysis:

The MG samples isolated from the one-pot and two-pot syntheses (above)were analyzed for viscosity analysis at various shear rates mostlyfollowing the procedures described below regarding CMG shear rateanalysis. The results of this experiment are listed in Table A.

TABLE A Viscosity of MG Solutions at Various Shear Rates ViscosityViscosity Viscosity Viscosity MG MG (cPs) @ (cPs) @ (cPs) @ (cPs) @Sample Loading 1 rpm 5 rpm 9 rpm 25 rpm 1 2% 8777 1874 1180 650 2  26628 2244 1522 —

The results summarized in Table A indicate that the viscosity of MGsolutions is reduced as shear rate is increased. This observation meansthat MG solutions demonstrate shear thinning behavior.

Preparation of Ethyl Poly Alpha-1,3-Glucan (EG)

20 g of poly alpha-1,3-glucan (M_(w)=245,000) was added to 200 mL ofisopropanol and 109 mL of 15 wt % sodium hydroxide in a 400-mL beakerwith a magnetic stir bar. The beaker was stirred on a magnetic stirplate at 375 rpm for one hour. The solid from this preparation was thencollected by vacuum filtration, mixed with 100 mL of acetone, and placedin a 200-mL capacity jar with a lid. This preparation sat overnightbefore being transferred to a 250-mL capacity shaker tube reactor. Thereactor was heated to 90° C. and charged with 85 g of ethyl chloride.The reaction was held at temperature for 17 hours. After cooling, thereaction was neutralized with 90% acetic acid. The solid was collectedby vacuum filtration, washed with 80% acetone five times, dried undervacuum at 20-25° C., and analyzed by NMR to determine DoS. The solidmaterial obtained was identified as EG with a DoS of 1.03.

Preparation of Quaternary Ammonium Poly Alpha-1,3-Glucan

10 g of poly alpha-1,3-glucan (M_(w)=168,000) was added to 100 mL ofisopropanol in a 500-mL capacity round bottom flask fitted with athermocouple for temperature monitoring and a condenser connected to arecirculating bath, and a magnetic stir bar. 30 mL of sodium hydroxide(17.5% solution) was added dropwise to this preparation, which was thenheated to 25° C. on a hotplate. The preparation was stirred for 1 hourbefore the temperature was increased to 55° C.3-chloro-2-hydroxypropyl-trimethylammonium chloride (31.25 g) was thenadded to provide a reaction, which was held at 55° C. for 1.5 hoursbefore being neutralized with 90% acetic acid. The solid thus formed(trimethylammonium hydroxypropyl poly alpha-1,3-glucan) was collected byvacuum filtration and washed with ethanol (95%) four times, dried undervacuum at 20-25° C., and analyzed by NMR and SEC to determine molecularweight and DoS.

Additional samples of trimethylammonium hydroxypropyl polyalpha-1,3-glucan were synthesized following the above process, but withcertain process variations. Specifically, poly alpha-1,3-glucan sampleswith various M_(w)'s were used as starting material, and differentamounts of etherification agent(3-chloro-2-hydroxypropyl-trimethylammonium chloride) were used. Also,reaction time (beginning from addition of etherification agent andending at neutralization) was varied. Table B lists these variousprocess variations and the resulting DoS measurements of the quaternaryammonium glucan ether products.

TABLE B DoS of Quaternary Ammonium Hydroxypropyl Poly Alpha-1,3-GlucanPrepared from Poly Alpha-1,3-Glucan M_(w) of poly alpha-1,3- glucanEtherification Reaction Sample starting Agent Time Designation materialAmount (hours) ^(a) DoS 1A 99231 31.25 g 3 1.26 1B-1 99231 31.25 g 10.59 1B-2 2 1.05 1B-3 4 1.29 1C-1 99231    9 g 1 0.39 1C-2 2 0.35 1C-3 40.31 1D 168000   15 g 2.5 0.43 1E-1 189558   18 g 1 0.34 1E-2 2 0.371E-3 4 0.45 1F 247182 31.25 g 4 0.17 1G 163200 31.25 g 3 0.52 1F 3408331.25 g 2.5 1.19 ^(a) Reaction time was measured from the timeetherification agent was added to the time of reaction neutralization.

Homogenization

Homogenization was performed using an IKA ULTRA TURRAX T25 DigitalHomogenizer (IKA, Wilmington, N.C.).

Preparation of Poly Alpha-1,3-Glucan Slurry and Wet Cake Using GtfJEnzyme

To prepare a slurry of poly alpha-1,3-glucan, an aqueous solution (0.75L) containing sucrose (100 g/L), potassium phosphate buffer (20 mM), andFermaSure® (500 ppm) was prepared and adjusted to pH 6.8-7.0. Thissolution was then charged with gtfJ enzyme extract (50 units/L). Theenzyme reaction solution was maintained at 20-25° C. for 48 hours. Aslurry was formed since the poly alpha-1,3-glucan synthesized in thereaction was aqueous insoluble.

The gtfJ enzyme reaction was performed as above to prepare a polyalpha-1,3-glucan wet cake. The poly alpha-1,3-glucan solids produced inthe reaction were collected using a Buchner funnel fitted with a325-mesh screen over 40-micrometer filter paper. The filtered polyalpha-1,3-glucan solids were resuspended in deionized water and filteredtwice more as above to remove sucrose, fructose and other low molecularweight, soluble by-products.

¹H Nuclear Magnetic Resonance (NMR) Method for Determining MolarSubstitution of Poly Alpha-1,3-Glucan Ether Derivatives

Approximately 30 mg of the poly alpha-1,3-glucan ether derivative wasweighed into a vial on an analytical balance. The vial was removed fromthe balance and 1.0 mL of deuterium oxide was added to the vial. Amagnetic stir bar was added to the vial and the mixture was stirred tosuspend the solid. Deuterated sulfuric acid (50% v/v in D₂O), 1.0 mL,was then added to the vial and the mixture was heated at 90° C. for 1hour in order to depolymerize and solubilize the polymer. The solutionwas allowed to cool to room temperature and then a 0.8 mL portion of thesolution was transferred into a 5-mm NMR tube using a glass pipet. Aquantitative ¹H NMR spectrum was acquired using an Agilent VNMRS 400 MHzNMR spectrometer equipped with a 5-mm Autoswitchable Quad probe. Thespectrum was acquired at a spectral frequency of 399.945 MHz, using aspectral window of 6410.3 Hz, an acquisition time of 3.744 seconds, aninter-pulse delay of 10 seconds and 64 pulses. The time domain data weretransformed using exponential multiplication of 0.50 Hz.

Two regions of the resulting spectrum were integrated for NMR analysisof hydroxypropyl poly alpha-1,3-glucan: an integral from 1.1 ppm to 1.4ppm, representative of the three methyl protons of all isopropyl groupspresent; and an integral from 4.7 ppm to 5.6 ppm, representative of theanomeric protons of the glucose rings. The integral of the isopropylmethyl region was divided by 3 to obtain a measure of the OCH₂CH(CH₃)Ogroups that were present. The molar substitution by the OCH₂CH(CH₃)Ogroups was then calculated by dividing the measure of the OCH₂CH(CH₃)Ogroups by the measure of all glucose rings present (the integral valueof the anomeric protons).

Two regions of the resulting spectrum were integrated for NMR analysisof methyl poly alpha-1,3-glucan: an integral from 3.0 ppm to 4.2 ppm wasrepresentative of the six glucan protons plus the OCH₃ protons, and anintegral from 4.6 ppm to 5.6 ppm was representative of the anomericprotons of the glucose rings. The integral of this latter region wasmultiplied by six to obtain the integral of the other six glucanprotons. The calculated integral for the six non-anomeric glucan protonswas subtracted from the integral of the 3.0 ppm to 4.2 ppm region toobtain the integral contribution of the OCH₃ protons. This integralvalue was divided by 3.0 to obtain a measure of the OCH₃ groups that arepresent. The degree of methylation was then calculated by dividing themeasure of the OCH₃ groups by the measure of all glucose rings present(the integral value of the anomeric protons).

Regarding NMR analysis of carboxymethyl poly alpha-1,3-glucan, thechemical shifts of the lines in the spectrum were referenced to thesignal for the alpha anomeric protons with no substitution at the C₂OH.This signal should be the third group of peaks from the left most edgeof the spectrum. The left-most signal in this group of peaks was set to5.222 ppm. Five regions of the referenced spectrum were integrated: anintegral from 5.44 ppm to 4.60 ppm represents all of the anomericprotons; the integrals from 4.46 ppm to 4.41 ppm and from 4.36 ppm to4.32 ppm were from the carboxymethyl CH₂ at the C₂ position adjacent toeither alpha or beta C1 HOH; the integral from 4.41 ppm to 4.36 ppm isfrom the carboxymethyl CH₂ at the C4 position; and the integral from4.24 ppm to 4.17 ppm was from the carboxymethyl CH₂ at the C6 position.The degree of carboxymethylation at the 2, 4, and 6 positions was thencalculated by dividing the integrals for the OCH₂COOH groups by two andthen dividing those results by the integration for all of the anomericprotons. A total degree of substitution was obtained by adding togetherthe three individual degrees of substitution.

Determination of Polymer Molecular Weight

The molecular weight of poly alpha-1,3-glucan ether derivatives wasdetermined by size exclusion chromatography (SEC) according to followingprotocol, unless otherwise indicated. Dry poly alpha-1,3-glucan etherderivative was dissolved in phosphate-buffered saline (PBS) (0.02-0.2mg/mL). The chromatographic system used was an Alliance™ 2695 liquidchromatograph from Waters Corporation (Milford, Mass.) coupled withthree on-line detectors: a differential refractometer 410 from Waters, amulti-angle light-scattering photometer Heleos™ 8+ from WyattTechnologies (Santa Barbara, Calif.), and a differential capillaryviscometer ViscoStar™ from Wyatt Technologies. The columns used for SECwere two Tosoh Haas Bioscience TSK GMPW_(XL) g3K and g4K G3000PW andG4000PW polymeric columns for aqueous polymers. The mobile phase wasPBS. The chromatographic conditions used were 30° C. at column anddetector compartments, 30° C. at sample and injector compartments, aflow rate of 0.5 mL/min, and injection volume of 100 μL. The softwarepackages used for data reduction were Astra version 6 from Wyatt (tripledetection method with column calibration).

Analysis of Polymer Molecular Weight by SEC (Table 3)

The molecular weight data disclosed in Table 3 below were obtained usingSEC with a differential refractive index detector. The instrument usedwas a WATERS ALLIANCE 2690 with a WATERS 2414 differential refractiveindex detector. The mobile phase was diluted PBS buffer (0.6 dilution: 6mmol/L phosphate buffer, 1.6 mmol/L potassium chloride, 80 mmol/L sodiumchloride, pH 7.4). The flow rate was 0.5 mL/min. The columns used weretwo TSK-GEL:GMPWXL and a guard column from Tosoh Bioscience (King ofPrussia, Pa.). Samples were prepared in the mobile phase at 10 mg/mL andinjection volume was 100 μL. Data were acquired and calculated usingEMPOWER software from Waters Corporation. The column set was calibratedusing a series of dextran standards from American Polymer Standards;thus, the molecular weight data in Table 3 are relative to dextran.

Enzyme-Mediated Hydrolysis Protocol

CMG or CMC polymer (100 mg) was added to a clean 20-mL glassscintillation vial equipped with a PTFE stir bar. Water (10.0 mL) thathad been previously adjusted to pH 7.0 using 5 vol % sodium hydroxide or5 vol % sulfuric acid was then added to the scintillation vial, and themixture was agitated until a solution (1 wt %) formed. A cellulase oramylase enzyme was added to the solution, which was then agitated for 24hours at room temperature (˜25° C.). Each enzyme-treated sample wasanalyzed by SEC (above). Negative controls were conducted as above, butwithout the addition of a cellulase or amylase.

Examples 1 and 2 below demonstrate the superior stability of polyalpha-1,3-glucan ether derivatives over cellulose ether derivatives inaqueous compositions comprising cellulase. Examples 3-5 belowdemonstrate adsorption of poly alpha-1,3-glucan ether derivatives ontovarious fabrics. Examples 6-21 below demonstrate viscosity- andrheology-modifying effects of poly alpha-1,3-glucan ether derivatives onaqueous compositions. All these features demonstrate applicability ofpoly alpha-1,3-glucan ether derivatives for use in various applicationssuch as in fabric care detergents (e.g., laundry detergent).

Examples 1-2 Effect of Cellulase on Carboxymethyl Poly Alpha-1,3-Glucan(CMG)

These examples disclose the superior stability of a polyalpha-1,3-glucan ether, CMG, in the presence of cellulase compared tocarboxymethyl cellulose (CMC).

Solutions (1 wt %) of CMC (M_(w)=90000, DoS=0.7) or CMG (M_(w)=101500,DoS=0.47, sample designation D102709-44 in Table 1) were treated withcellulase or amylase (Table 3) following the above-described procedure.CMC M_(w) decreased by over 60% when treated with cellulase for 24 hours(Table 3, Example 1.1). Conversely, CMG polymer M_(w) was reduced byonly 1.1% and 10.6% when treated with cellulase (Table 3, Examples 2.1and 2.4, respectively). Both CMC and CMG were stable against degradationby amylase (Table 3, Examples 1.2, 2.2 and 2.3). Control polymersolutions underwent the same treatment protocol, with the exception thatneither a cellulase or amylase were included in the treatment. Thecontrols indicate that the 24-hour agitation aspect of the abovetreatment protocol marginally reduced molecular weight of both CMG andCMC.

TABLE 3 Measuring Stability of CMG and CMC Against Degradation byCellulase or Amylase Percent Ex- Poly- Enzyme Enzyme M_(n) M_(w) Degra-ample mer Enzyme Type Loading (K) (K) dation^(a) 1 CMC none N/A — 51.488.7 (con- trol) 1.1 CMC PURADAX Cellulase 1 mg/mL 12.7 33.3 62.5 HA1200E 1.2 CMC PREFERENZ Amylase 3 μL/mL 44.8 83.7 5.6 S 100 2 CMG noneN/A — 49.1 108.1 (con- trol) 2.1 CMG PURADAX Cellulase 1 mg/mL 46.8106.9 1.1 HA 1200E 2.2 CMG PREFERENZ Amylase 3 μL/mL 48.5 105.2 2.7 S100 2.3 CMG PURASTAR Amylase 3 μL/mL 44.3 103.6 4.2 ST L 2.4 CMG PURADAXCellulase 3 μL/mL 45 96.6 10.6 EG L ^(a)Percent degradation of polymerM_(w) by cellulase or amylase.

The data in Table 3 indicate that CMC is highly susceptible todegradation by cellulase, whereas CMG is resistant to this degradation.Since high polymer molecular weight is a key characteristic of a solublepolysaccharide ether for providing viscosity to aqueous compositions,use of CMC for providing viscosity to an aqueous composition (e.g.,laundry or dishwashing detergent) containing cellulase would beunacceptable.

Examples 6-19 below show that CMG and other types of polyalpha-1,3-glucan ether derivatives act as viscosity and rheologymodifiers of aqueous compositions. Thus, given the resistance of CMG tocellulase activity, this poly alpha-1,3-glucan ether derivative would bevery useful for providing viscosity to cellulase-containing aqueouscompositions such as detergents. It is reasonable to conclude that thisresult similarly applies to other poly alpha-1,3-glucan etherderivatives.

Example 3 Creating Calibration Curves for Direct Red 80 and ToluidineBlue 0 Dyes Using UV Absorption

This example discloses creating calibration curves useful fordetermining the relative level of adsorption of poly alpha-1,3-glucanether derivatives onto fabric surfaces.

Solutions of known concentration (ppm) were made using Direct Red 80 andToluidine Blue O dyes. The absorbance of these solutions was measuredusing a LAMOTTE SMART2 Colorimeter at either 520 or 620 nm. Theabsorption information was plotted in order that it could be used todetermine dye concentration of solutions which were exposed to fabricsamples. The concentration and absorbance of each calibration curve areprovided in Tables 4 and 5.

TABLE 4 Direct Red 80 Dye Calibration Curve Data Dye AverageConcentration Absorbance (ppm) @520 nm 25 0.823333333 22.5 0.79666666720 0.666666667 15 0.51 10 0.37 5 0.2

TABLE 5 Toluidine Blue O Dye Calibration Curve Data Dye AverageConcentration Absorbance (ppm) @620 nm 12.5 1.41 10 1.226666667 7 0.88 50.676666667 3 0.44 1 0.166666667

Thus, calibration curves were prepared that are useful for determiningthe relative level of adsorption of poly alpha-1,3-glucan etherderivatives onto fabric surfaces. These calibration curves were utilizedin Examples 4 and 5.

Example 4 Adsorption of Quaternary Ammonium Poly Alpha-1,3-Glucan Etheron Various Fabrics

This example discloses testing the degree of adsorption of a quaternaryammonium poly alpha-1,3-glucan (trimethylammonium hydroxypropyl polyalpha-1,3-glucan) on different types of fabrics.

A 0.07 wt % solution of trimethylammonium hydroxypropyl polyalpha-1,3-glucan (Sample 1 F, Table B, General Methods) was made bydissolving 0.105 g of the polymer in 149.89 g of deionized water. Thissolution was divided into several aliquots with different concentrationsof polymer and other components (Table 6). Such other components wereacid (dilute hydrochloric acid) or base (sodium hydroxide) to modify pH,or NaCl salt.

TABLE 6 Quaternary Ammonium Poly Alpha-1,3-GlucanSolutions Used inFabric Adsorption Studies Amount Amount of Polymer Amount Amount of NaClSolution Concentration of Acid of Base Final (g) (g) (wt %) (g) (g) pH 015 0.07 n/a n/a ~7 0.15 14.85 0.0693 n/a n/a ~7 0.3 14.7 0.0686 n/a n/a~7 0.45 14.55 0.0679 n/a n/a ~7 0 9.7713 0.0683 0.2783 n/a 2.92 0 9.77240.0684 0.2369 n/a 4.96 0 10.0311 0.0702 n/a 0.0319 9.04 0 9.9057 0.0693n/a 0.1059 11.05

Four different fabric types (cretonne, polyester, 65:35polyester/cretonne, bleached cotton) were cut into 0.17 g pieces. Eachpiece was placed in a 2-mL well in a 48-well cell culture plate. Eachfabric sample was exposed to 1 mL of each of the above solutions (Table6) for a total of 36 samples (a control solution with no polymer wasincluded for each fabric test). The fabric samples were allowed to sitfor at least 30 minutes in the polymer solutions. The fabric sampleswere removed from the polymer solutions and rinsed in DI water for atleast one minute to remove any unbound polymer. The fabric samples werethen dried at 60° C. for at least 30 minutes until constant dryness wasachieved. The fabric samples were weighed after drying and individuallyplaced in 2-mL wells in a clean 48-well cell culture plate. The fabricsamples were then exposed to 1 mL of a 250 ppm Direct Red 80 dyesolution. The samples were left in the dye solution for at least 15minutes. Each fabric sample was removed from the dye solution,afterwhich the dye solution was diluted 10×.

The absorbance of the diluted solutions was measured compared to acontrol sample. A relative measure of glucan polymer adsorbed to thefabric was calculated based on the calibration curve created in Example3 for Direct Red 80 dye. Specifically, the difference in UV absorbancefor the fabric samples exposed to polymer compared to the controls(fabric not exposed to polymer) represents a relative measure of polymeradsorbed to the fabric. This difference in UV absorbance could also beexpressed as the amount of dye bound to the fabric (over the amount ofdye bound to control), which was calculated using the calibration curve(i.e., UV absorbance was converted to ppm dye). Table 7 provides “dye(ppm)”; a positive value represents the dye amount that was in excess tothe dye amount bound to the control fabric, whereas a negative valuerepresents the dye amount that was less than the dye amount bound to thecontrol fabric. A positive value reflects that the glucan ether compoundadsorbed to the fabric surface.

TABLE 7 Relative Amount of Quaternary Ammonium Poly Alpha-1,3-GlucanBound to Different Fabrics Under Different Conditions 65:35 BleachedCretonne Polyester Polyester/Cretonne Cotton Salt dye Salt dye Salt dyeSalt dye Conc. (ppm)^(a) Conc. (ppm)^(a) Conc. (ppm)^(a) Conc. (ppm)^(a)0^(b) +4.56 0^(b) +0.48 0b +1.27 0^(b) +3.13 1%^(b) +1.97 1%^(b) +0.461%^(b) +0.58 1%^(b) +3.78 2%^(b) −0.52 2%^(b) +0.0003 2%^(b) +0.162%^(b) +4.11 3%^(b) 0 3%^(b) +0.10 3%^(b) +0.07 3%^(b) −0.13 pH^(c)pH^(c) pH^(c) pH^(c) 3 +2.06 3 −0.29 3 −0.26 3 +2.97 5 +3.13 5 +0.13 5−0.33 5 +2.87 9 +2.05 9 −0.003 9 +0.07 9 +4.69 11 +2.02 11 −0.59 11+0.12 11 +2.03 ^(a)Amount of dye bound to fabric. A positive valuerepresents the dye amount that was in excess to the dye amount bound tocontrol. A positive dye amount in turn represents the relative amount ofglucan ether adsorbed to the fabric. ^(b)The pH of binding conditionswas about 7 (refer to Table 6). ^(c)Binding conditions did not includesalt (refer to Table 6).

The data in Table 7 indicate that quaternary ammonium glucan polymer canadsorb to various types of fabric under different salt and pHconditions. This adsorption occurs even though the fabrics were rinsedafter exposure to the polymer. It is notable that the glucan ether wasable to adsorb to polyester and the polyester/cretonne blend, inaddition to adsorbing to cotton.

Thus, a poly alpha-1,3-glucan ether derivative in an aqueous compositioncan adsorb to fabric. This adsorption reflects that cationic glucanether derivatives should be useful in detergents for fabric care (e.g.,as anti-redeposition agents).

Example 5 Adsorption of Carboxymethyl Poly Alpha-1,3-Glucan (CMG) onVarious Fabrics

This example discloses testing the degree of adsorption of a polyalpha-1,3-glucan ether compound (CMG) on different types of fabrics.

A 0.25 wt % solution of CMG was made by dissolving 0.375 g of thepolymer in 149.625 g of deionized water. This solution was divided intoseveral aliquots with different concentrations of polymer and othercomponents (Table 8). Such other components were acid (dilutehydrochloric acid) or base (sodium hydroxide) to modify pH, or NaClsalt.

TABLE 8 CMG Solutions Used in Fabric Adsorption Studies Amount Amount ofPolymer Amount Amount of NaCl Solution Concentration of Acid of BaseFinal (g) (g) (wt %) (g) (g) pH 0 15 0.25 n/a n/a ~7 0.15 14.85 0.2475n/a n/a ~7 0.3 14.7 0.245 n/a n/a ~7 0.45 14.55 0.2425 n/a n/a ~7 09.8412 0.2459 0.1641 n/a 3.52 0 9.4965 0.2362 0.553 n/a 5.01 0 9.5180.2319 n/a 0.752 8.98 0 9.8811 0.247 n/a 0.1189 10.93

Four different fabric types (cretonne, polyester, 65:35polyester/cretonne, bleached cotton) were cut into 0.17 g pieces. Eachpiece was placed in a 2-mL well in a 48-well cell culture plate. Eachfabric sample was exposed to 1 mL of each of the above solutions (Table8) for a total of 36 samples (a control solution with no polymer wasincluded for each fabric test). The fabric samples were allowed to sitfor at least 30 minutes in the polymer solutions. The fabric sampleswere removed from the polymer solutions and rinsed in DI water for atleast one minute to remove any unbound polymer. The fabric samples werethen dried at 60° C. for at least 30 minutes until constant dryness wasachieved. The fabric samples were weighed after drying and individuallyplaced in 2-mL wells in a clean 48-well cell culture plate. The fabricsamples were then exposed to 1 mL of a 250 ppm Toluidine Blue dyesolution. The samples were left in the dye solution for at least 15minutes. Each fabric sample was removed from the dye solution,afterwhich the dye solution was diluted 10×.

The absorbance of the diluted solutions was measured compared to acontrol sample. A relative measure of glucan polymer adsorbed to thefabric was calculated based on the calibration curve created in Example3 for Toluidine Blue dye. Specifically, the difference in UV absorbancefor the fabric samples exposed to polymer compared to the controls(fabric not exposed to polymer) represents a relative measure of polymeradsorbed to the fabric. This difference in UV absorbance could also beexpressed as the amount of dye bound to the fabric (over the amount ofdye bound to control), which was calculated using the calibration curve(i.e., UV absorbance was converted to ppm dye). Table 9 provides “dye(ppm)”; a positive value represents the dye amount that was in excess tothe dye amount bound to the control fabric, whereas a negative valuerepresents the dye amount that was less than the dye amount bound to thecontrol fabric. A positive value reflects that the glucan ether compoundadsorbed to the fabric surface.

TABLE 9 Relative Amount of CMG Bound to Different Fabrics UnderDifferent Conditions 65:35 Bleached Cretonne PolyesterPolyester/Cretonne Cotton Salt dye Salt dye Salt dye Salt dye Conc.(ppm)^(a) Conc. (ppm)^(a) Conc. (ppm)^(a) Conc. (ppm)^(a) 0^(b) 0.290^(b) 0 0^(b) 0 0b +9.28 1%^(b) +2.25 1%^(b) +5.18 1%^(b) +0.49 1%^(b)+6.26 2%^(b) −0.19 2%^(b) +3.62 2%^(b) +1.76 2%^(b) +5.57 3%^(b) +1.373%^(b) +1.47 3%^(b) +1.76 3%^(b) +7.62 pH^(c) pH^(c) pH^(c) pH^(c) 3.5−1.47 3.5 +1.76 3.5 −0.39 3.5 +3.22 5 +0.02 5 +7.62 5 −1.17 5 +10.17 9+0.78 9 +1.36 9 −1.95 9 +17.11 11 +4.39 11 +0.78 11 +2.54 11 +15.73^(a)Amount of dye bound to fabric. A positive value represents the dyeamount that was in excess to the dye amount bound to control. A positivedye amount in turn represents the relative amount of glucan etheradsorbed to the fabric. ^(b)The pH of binding conditions was about 7(refer to Table 8). ^(c)Binding conditions did not include salt (referto Table 8).

The data in Table 9 indicate that CMG polymer can adsorb to varioustypes of fabric under different salt and pH conditions. This adsorptionoccurs even though the fabrics were rinsed after exposure to thepolymer. It is notable that the glucan ether was able to adsorb topolyester and the polyester/cretonne blend, considering thatcarboxymethyl cellulose does not absorb to, or only poorly adsorbs to,polyester and blends thereof with cotton (see European Pat. Appl. Publ.No. EP0035478, for example).

Thus, a poly alpha-1,3-glucan ether derivative in an aqueous compositioncan adsorb to fabric. This adsorption reflects that glucan etherderivatives should be useful in detergents for fabric care (e.g., asanti-redeposition agents).

Example 6 Effect of Dissolution Method on Viscosity of CarboxymethylPoly Alpha-1,3-Glucan (CMG) Solutions

This Example describes the viscosity of CMG solutions prepared usingdifferent dissolution techniques.

A sample of CMG (1G, Table 1) was prepared as described in the GeneralMethods and then dissolved using three different methods:

a) Homogenization: 1 g of CMG (1G) was added to de-ionized (DI) water(49 g) to provide a 2 wt % CMG preparation, which was then homogenizedfor 12-15 seconds at 20,000 rpm to dissolve the CMG. No filtering wasneeded because there were no particulates in the solution.

b) Mechanical mixing: DI water (49 g) was stirred at 400 rpm using anoverhead mixer equipped with a propeller blade. 1 g of CMG (1G) wasgradually added to the vortex created by the mixer to provide a 2 wt %CMG preparation, which was then warmed to 25° C. using a water bath anda hot plate to obtain uniform heating. The preparation was stirred untilall CMG was dissolved. The resulting solution was then filtered byvacuum to remove any particulate material.

c) Manual shaking: 1 g of the CMG (1G) was added to 49 g of DI water toprovide a 2 wt % CMG preparation, which was then shaken by hand for10-15 seconds and allowed to sit overnight to complete dissolution. Theresulting solution was then filtered by vacuum to remove any particulatematerial.

To determine the viscosity of each CMG solution at various shear rates,dissolved CMG samples were subjected to 10, 60, 150, and 250 rpm shearrates using a Brookfield III+ Rheometer equipped with a recirculatingbath to control temperature (20° C.) and a SC4-21 Thermosel® spindle.The shear rate was increased using a gradient program which increasedfrom 10-250 rpm and the shear rate was increased by 4.9 (1/s) every 20seconds. The results of this experiment are listed in Table 10.

TABLE 10 Effect of Dissolution Method on the Viscosity of CMG CMG CMGViscosity Viscosity Viscosity Viscosity Sam- Load- Dissolution (cPs) @(cPs) @ (cPs) @ (cPs) @ ple ing Method 10 rpm 60 rpm 150 rpm 250 rpm 1G2% Manual 405.7 317.69 201.3 168.8 Shaking 1G 2% Mechanical 827.7 304.3196.4 161.6 stirring 1G 2% Homogenizer 8379.3 980.7 442.4 327.2

The results summarized in Table 10 indicate that the method ofdissolving CMG can have an effect on the viscosity of the solution. Thesamples that were either manually shaken or mechanically stirred showedlower viscosity compared to the sample that was homogenized. It appearsthat the filtration step that followed manual shaking or mechanicalstirring has a dramatic effect on reducing the viscosity.

Thus, a solution of CMG prepared by homogenization had greater viscositycompared to CMG solutions prepared by manual shaking and mechanicalstirring.

Example 7 Effect of Shear Rate on Viscosity of CMG

This Example describes the effect of shear rate on the viscosity ofvarious CMG solutions, where the solutions were prepared using CMG withdifferent molecular weights. It is shown that CMG solutions exhibitsignificant shear thinning behavior. Thus, addition of CMG to a liquidcan modify the rheological behavior of the liquid.

Various solutions of CMG with different molecular weights were preparedas described in Example 6 by homogenization. Specifically, to prepare a2 wt % solution of each of these samples, 1 g of CMG (particular samplesfrom Table 1) was added to 49 g of DI water. Each preparation was thenhomogenized for 12-15 seconds at 20,000 rpm to dissolve the CMG.

The viscosity of each CMG solution was measured as in Example 6. Theresults of this experiment are listed in Table 11.

TABLE 11 Viscosity of CMG Solutions with Different Molecular Weights atVarious Shear Rates Viscosity Viscosity Viscosity Viscosity CMG CMG(cPs) @ (cPs) @ (cPs) @ (cPs) @ Sample Loading 10 rpm 60 rpm 150 rpm 250rpm 1C 2% 93 73 64 60 1D 2% 10 10 10 10 1E 2% 1242 713.9 504 414.6 1F 2%5393 1044 656 454 1J 2% 8379.3 980.7 442.4 327.2

The results summarized in Table 11 indicate that the viscosity of mostof the CMG solutions is reduced as the shear rate is increased. Thisobservation means that CMG solutions demonstrate significant shearthinning behavior.

Thus, CMG when dissolved in an aqueous solution not only modifies theviscosity of the solution, but also the rheological properties of thesolution. CMG can therefore be added to an aqueous liquid to modify itsrheological profile.

Example 8 Effect of Temperature on Viscosity

This Example describes the effect of temperature on the viscosity of CMGsolutions.

A 2 wt % solution of CMG (1G, Table 1) was prepared as described inExample 6 using the homogenization method. The viscosity of the CMGsolution was measured using a Brookfield DV III+ Rheometer equipped witha recirculating bath to control temperature and a SC4-21 Thermosel®spindle. The shear rate was held constant at 60 rpm while thetemperature was increased by 2° C. every 2 minutes. The temperature wasincreased from 20° C. to 70° C. and viscosity measurements were taken atcertain temperatures. The results are shown in Table 12.

TABLE 12 Effect of Temperature on the Viscosity of CMG SolutionsViscosity Temperature (cPs) @ 60 (° C.) rpm 20 784.3 40 491.4 50 435.660 404.6 70 365.8

The results summarized in Table 12 indicate a decrease in viscosity asthe temperature is increased.

Example 9 Effect of Degree of Substitution on Viscosity

This Example describes the effect of DoS of CMG on the viscosity of CMGin solution.

Two solutions of 2 wt % CMG (1G and 1H, Table 1) were prepared asdescribed in Example 6 using the homogenization method. The viscosity ofeach solution was measured according to Example 6 and the results areshown in Table 13.

TABLE 13 Effect of Degree of Substitution on Viscosity ViscosityViscosity Viscosity Viscosity CMG (cPs) @ (cPs) @ 60 (cPs) @ (cPs) @Sample DoS 10 rpm rpm 150 rpm 250 rpm 1G 0.5 8379.3 980.8 442.4 327.2 1H0.9 n/a n/a 61.8 57.2

The results summarized in Table 13 indicate that as the DoS of the CMGpolymer is increased, there is a decrease in viscosity. Note that theBrookfield Rheometer was not capable of accurately measuring theviscosity at low shear rates (10 and 60 rpm) for the CMG with DoS 0.9.However, as the shear rate was increased to 150 rpm and 250 rpm for thisCMG, the torque on the instrument increased and the viscositymeasurement became reliable.

Thus, CMG with a lower DoS has greater viscosifying activity than CMGwith a higher DoS.

Example 10 Effect of pH on Viscosity of CMG

This Example describes the effect of pH on the viscosity of CMG insolution.

A solution of 2 wt % CMG (1G, Table 1) was prepared as described inExample 6 using the homogenization method. The solution was divided intofour aliquots, which were adjusted to pH 3.5, pH 4.5, pH 4.8 or pH 5.0using citric acid.

A second solution of 2 wt % CMG (1G, Table 1) was prepared as in Example6 using the homogenization method. The solution was divided into twoaliquots. One aliquot was adjusted to pH 3.0 using citric acid and thesecond aliquot was adjusted to pH 12 using sodium hydroxide.

The viscosity of each of the above preparations was measured accordingto Example 6 and the results are shown in Table 14.

Solutions of 1 wt %, 1.5 wt %, or 2 wt % CMG (11 and 1J, Table 1) wereprepared as in Example 6 using the homogenization method. The solutionswere then adjusted to pH 3, pH 3.5, pH 4, pH 5, pH 6, or pH 7 usingglacial acetic acid. The viscosity of certain preparations was measuredaccording to Example 6 (results shown in Table 14), but with thefollowing modifications. Certain viscosity measurements were made usinga Brookfield III+ Rheometer equipped with either a SC4-21 or SC4-18Thermosel® spindle. Viscosity measurements were made at 10 rpm, 58.98rpm, 152 rpm and 232.5 rpm shear rates.

TABLE 14 Viscosity of CMG Solutions at Various pHs Vis- Vis- Vis- Vis-cosity cosity cosity cosity CMG CMG (cPs) @ (cPs) @ (cPs) @ (cPs) @ Sam-Load- 10 60 150 250 ple ing pH Spindle rpm rpm rpm rpm 1G 2% 3.0 SC4-21223.2 66.2 34.9 27.6 1G 2% 3.5 SC4-21 2064.6 1255.1 n/a 440 1G 2% 4.5SC4-21 6891.3 1573.7 607.6 386.8 1G 2% 4.8 SC4-21 10230 1734.5 673 4401G 2% 5.0 SC4-21 7328.4 1447.5 509.7 333.6 1G 2% 12 SC4-21 2325 636.3302.2 216 Vis- Vis- Vis- Vis- cosity cosity cosity cosity CMG (cPs)(cPs) @ (cPs) @ (cPs) @ Sam- Load- @ 58.98 152.0 232.5 ple ing pHSpindle 10 rpm rpm rpm rpm 1I   1% 3.5 SC4-18 1799.4 388.17 213.42142.26 1I   1% 4.0 SC4-18 1140.48 325.14 145.06 109.82 1I   1% 5.0SC4-18 n/a 187.64 90.59 72.99 1I   1% 6.0 SC4-18 n/a 118.89 91.15 76.371I   1% 7.0 SC4-18 n/a 190.5 127.83 98.33 1I   2% 3.0 SC4-21 120 97.7659.35 47.6 1I   2% 3.5 SC4-21 3720 1354.48 n/a n/a 1I   2% 4.0 SC4-216454.2 n/a n/a n/a 1I   2% 5.0 SC4-21 9197.7 1351.32 534.14 n/a 1I   2%6.0 SC4-21 7030.8 1256.71 460.72 354.4 1J   2% 3.5 SC4-18 3505.92 658.88334.59 234.18 1J   2% 4.0 SC4-18 3269.38 658.88 307.91 216.27 1J   2%5.0 SC4-18 3970.56 671.77 278.45 183.15 1J   2% 7.0 SC4-21 3840.9 622.84351.2 263.2 1J   2% 5.0 SC4-21 4175.7 668.57 324.28 222.4 1J   2% 4.0SC4-21 7008.9 763.17 313.88 273.6 1J 1.5% 4.0 SC4-18 2289.41 388.17181.19 126.72 1J 1.5% 5.0 SC4-18 n/a 217.72 110.05 88.54

The results summarized in Table 14 for CMG sample 1G indicate aviscosity decrease at pH 3.5. The viscosity of the CMG (1G) solutions atpH levels above 4.5 indicated no decrease in viscosity, except that atpH 12 there was a slight decrease in viscosity.

The pH of each of the CMG solutions in the above procedure was adjustedfollowing the preparation of each solution. To examine if the order ofaddition of the acid for pH adjustment had any impact on the viscosityof the solution, DI water was adjusted to pH 3 using citric acid. A 2 wt% solution of CMG (1G, Table 1) was prepared using the pH 3 DIwater/citric acid and homogenized according to Example 6 to dissolve thepolymer. The viscosity of this solution was measured as in Example 6 andis listed in Table 15.

TABLE 15 Viscosity of CMG Solution—Reverse Addition of Acid for pHAdjustment Viscosity Viscosity Viscosity Viscosity CMG CMG (cPs) @ (cPs)@ (cPs) @ (cPs) @ Sample Loading pH 10 rpm 60 rpm 150 rpm 250 rpm 1G 2%3 9188.4 1444.4 665.1 416.8

The results summarized in Table 15 indicate that when the water ispH-adjusted before the CMG polymer is dissolved, the viscosity is stable(i.e., the viscosity values in Table 15 at each respective shear rateare greater than those listed in the top row of Table 14). This could bedue to a buffering effect of the polymer.

Thus, pH affects the viscosity of CMG solutions.

Example 11 Effect of Sodium Chloride on the Viscosity of CMG

This Example describes the effect of sodium chloride on the viscosity ofCMG in solution.

A 2 wt % solution of CMG (1G, Table 1) was prepared by adding 3 g of CMGto 147 g of DI water as described in Example 6 using the homogenizationmethod. The CMG solution thus prepared was divided into three aliquots,each weighing 49.98 g, 49.84 g, and 45.63 g, respectively. Sodiumchloride (0.025 g) was added to the 49.98 g CMG solution to make asolution of 2 wt % CMG in 0.05 wt % sodium chloride. Sodium chloride(0.15 g) was added to the 49.84 g CMG solution to make a solution of 2wt % CMG in 0.3 wt % sodium chloride. Sodium chloride (0.47 g) was addedto the 45.63 g CMG solution to make a solution of 2 wt % CMG in 1 wt %sodium chloride. The viscosity levels of each of the solutions weremeasured as described in Example 6 and are shown in Table 16.

To determine if the order of addition of sodium chloride had any effecton the final viscosity of the CMG solution, a 1% solution of sodiumchloride was made by dissolving 0.5 g of sodium chloride in 49.5 g of DIwater. CMG (1 g) was added to 49 g of the 1% sodium chloride using thehomogenization method as described in Example 6. The viscosity of thesolution was measured as described in Example 6 and is shown as sample1G-1 in Table 16.

TABLE 16 Effect of Sodium Chloride on CMG Viscosity Sodium ViscosityViscosity Viscosity Viscosity CMG CMG Chloride (cPs) @ (cPs) @ (cPs) @(cPs) @ Sample Loading Conc. 10 rpm 60 rpm 150 rpm 250 rpm 1G 2% 0.05%n/a 316.9 219 206 1G 2%  0.3% 957.9 484.1 301.6 261.2 1G 2%    1% 1236.2567.6 366.5 302 1G-1 2%    1% 1795.9 539.2 299.7 221.2

The results summarized in Table 16 indicate that neither the presence ofsodium chloride nor the method of its addition to the CMG solution havea significant impact on the viscosity of CMG in solution.

Example 12 Effect of Sodium Sulfate on the Viscosity of CMG

This Example describes the effect of sodium sulfate on the viscosity ofCMG in solution.

A 2 wt % solution of CMG (1G, Table 1) was prepared as described inExample 6 using the homogenization method. This solution was thendivided into three portions each weighing 30.00 g, 29.69 g, and 29.92 g,respectively. Sodium sulfate (0.014 g) was dissolved in the 30.00 g CMGsolution to make a solution of 2 wt % CMG in 0.047 wt % sodium sulfate.Sodium sulfate (0.088 g) was dissolved in the 29.69 g solution of CMG tomake a solution of 2 wt % CMG in 0.3 wt % sodium sulfate. Sodium sulfate(0.29 g) was dissolved in the 29.92 g CMG solution to make a solution of2 wt % CMG in 0.96 wt % sodium sulfate. The viscosity levels of each ofthe solutions were measured as described in Example 6 and are shown inTable 17.

TABLE 17 Effect of Sodium Sulfate on CMG Viscosity CMG CMG SodiumViscosity Viscosity Viscosity Viscosity Sam- Load- Sulfate (cPs) @ (cPs)@ (cPs) @ (cPs) @ ple ing Conc. 10 rpm 60 rpm 150 rpm 250 rpm 1G 2%0.05% 1292.7 559.8 290.6 230.8 1G 2%  0.3% 4640.7 640.2 310.8 237.6 1G2%   1% 5245.2 774.2 331.62 246.4

The results summarized in Table 17 indicate that the presence of sodiumsulfate did not have a significant impact on the viscosity of CMG insolution.

Example 13 Effect of Sucrose on the Viscosity of CMG

This Example describes the effect of sucrose on the viscosity of CMG insolution.

A 2 wt % solution of CMG (1G, Table 1) was prepared as described inExample 6 using the homogenization method. This solution was dividedinto two portions each weighing 45 g and 20 g, respectively. To preparea 10 wt % solution of sucrose in CMG, 5 g of sucrose was dissolved in 45g of the CMG solution. For a 60 wt % solution of sucrose in CMG, 30 g ofsucrose was dissolved by hand mixing with 20 g of the CMG solution. Theviscosity levels of each of the solutions were measured as described inExample 6 and are shown in Table 18.

TABLE 18 Effect of Sucrose on CMG Viscosity Viscosity ViscosityViscosity Viscosity CMG CMG Sucrose (cPs) @ (cPs) @ (cPs) @ (cPs) @Sample Loading Conc. 10 rpm 60 rpm 150 rpm 250 rpm 1G 2% 10% 7151.71067.5 430.7 322.8 1G 2% 60% 4278 n/a n/a n/a

The results summarized in Table 18 indicate that the presence of 10%sucrose does not have any impact on the viscosity of the CMG. However,an increased amount of sucrose (60%) decreased the viscosity.

Example 14 Effect of Shear Rate on Viscosity of Potassium/Sodium CMG

This Example describes the effect of shear rate on the viscosity ofpotassium/sodium CMG (KNaCMG) in solution. It is shown that KNaCMG insolution exhibits significant shear thinning behavior. Thus, addition ofKNaCMG to a liquid can modify the rheological behavior of the liquid.

A KNaCMG sample was prepared as described in the General Methods. Toprepare a 2 wt % solution of KNaCMG, 1 g of KNaCMG was added to 49 g ofDI water. This preparation was then homogenized for 12-15 seconds at20,000 rpm to dissolve the KNaCMG.

To determine the viscosity of the KNaCMG solution at various shearrates, KNaCMG samples were subjected to various shear rates using aBrookfield III+ Rheometer equipped with a recirculating bath to controltemperature (20° C.) and a YULA15-E(Z) spindle. The shear rate wasincreased using a gradient program which increased from 0.01-250 rpm andthe shear rate was increased by 7.36 (1/s) every 20 seconds. The resultsof this experiment are listed in Table 19.

TABLE 19 Viscosity of KNaCMG Solution at Various Shear Rates ViscosityViscosity Viscosity Viscosity KNaCMG (cPs) @ (cPs) @ (cPs) @ (cPs) @Loading 22.07 rpm 80.89 rpm 161.8 rpm 250 rpm 2% 108.52 82.06 69.4762.12

The results summarized in Table 19 indicate that the viscosity of theKNaCMG solution is reduced as the shear rate is increased. Thisobservation means that KNaCMG solutions demonstrate significant shearthinning behavior.

Thus, KNaCMG when dissolved in an aqueous solution not only modifies theviscosity of the solution, but also the rheological properties of thesolution. KNaCMG can therefore be added to an aqueous liquid to modifyits rheological profile.

The procedure in this Example could easily be adapted to use potassiumcarboxymethyl poly alpha-1,3-glucan (KCMG) instead of KNaCMG.

Example 15 Effect of Shear Rate on Viscosity of Lithium/Sodium CMG

This Example describes the effect of shear rate on the viscosity oflithium/sodium CMG (LiNaCMG) in solution. It is shown that LiNaCMG insolution exhibits significant shear thinning behavior. Thus, addition ofLiNaCMG to a liquid can modify the rheological behavior of the liquid.

To prepare a 2 wt % solution of LiNaCMG, 1 g of LiNaCMG (sample 2A,General Methods) was added to 49 g of DI water. This preparation wasthen homogenized for 12-15 seconds at 20,000 rpm to dissolve theLiNaCMG.

To determine the viscosity of the LiNaCMG solution at various shearrates, LiNaCMG samples were subjected to various shear rates using aBrookfield III+ Rheometer equipped with a recirculating bath to controltemperature (20° C.) and a YULA15-E(Z) spindle. The shear rate wasincreased using a gradient program which increased from 0.01-250 rpm andthe shear rate was increased by 7.36 (1/s) every 20 seconds. The resultsof this experiment are listed in Table 20.

TABLE 20 Viscosity of LiNaCMG Solution at Various Shear Rates ViscosityViscosity Viscosity Viscosity LiNaCMG LiNaCMG (cPs) @ (cPs) @ (cPs) @(cPs) @ Sample Loading 44.13 rpm 80.89 rpm 161.8 rpm 250 rpm 2A 2% 37.635.22 31.83 29.62

The results summarized in Table 20 indicate that the viscosity of theLiNaCMG solution is reduced as the shear rate is increased. Thisobservation means that LiNaCMG solutions demonstrate significant shearthinning behavior.

Thus, LiNaCMG when dissolved in an aqueous solution not only modifiesthe viscosity of the solution, but also the rheological properties ofthe solution. LiNaCMG can therefore be added to an aqueous liquid tomodify its rheological profile.

The procedure in this Example could easily be adapted to use lithiumcarboxymethyl poly alpha-1,3-glucan (LiCMG) instead of LiNaCMG.

Example 16 Effect of Shear Rate on Viscosity of Methyl PolyAlpha-1,3-Glucan

This Example describes the effect of shear rate on the viscosity of MG.It is shown that MG exhibits shear thinning behavior. Thus, addition ofMG to a liquid can modify the rheological behavior of the liquid.

To prepare a 2 wt % solution of MG, 1 g of Sample 1 or 2 (GeneralMethods) was added to 49 g of DI water. Each preparation was thenhomogenized for 15-30 seconds at 20,000 rpm to dissolve the MG.

To determine the viscosity of each MG solution at various shear rates,MG samples were subjected to 10-250 rpm shear rates using a BrookfieldDV III+ Rheometer equipped with a recirculating bath to controltemperature (20° C.) and an SC4-21 Thermosel® spindle or ULA (ultra lowadapter) spindle and adapter set. The shear rate was increased using agradient program which increased from 10-250 rpm. The shear rate wasincreased by 7.35 (1/s) every 20 seconds for the ULA spindle andadapter, and by 4.9 (1/s) every 20 seconds for the SC4-21 spindle. Theresults of this experiment are listed in Table 21.

TABLE 21 Viscosity of MG Solutions at Various Shear Rates MG MGViscosity Viscosity Viscosity Viscosity Sam- Load- (cPs) @ (cPs) @ (cPs)@ (cPs) @ ple ing Spindle 14.72 rpm 66.18 rpm 154.4 rpm 250 rpm 1 2% ULAN/A 24.84 23.42 22.67 2 2% ULA 254.17 228.97 N/A N/A 2 1% ULA N/A 24.3625.5 25.92 MG MG Viscosity Viscosity Viscosity Viscosity Sam- Load-(cPs) @ (cPs) @ (cPs) @ (cPs) @ ple ing Spindle 14.9 rpm 63.88 rpm 152.0rpm 232.5 rpm 2 2% SC4-21 193.49 257.69 226.38 208.0

The results summarized in Table 21 indicate that the viscosity of the MGsolutions is reduced as the shear rate is increased. This observationmeans that MG solutions demonstrate shear thinning behavior.

Thus, MG when dissolved in an aqueous solution not only modifies theviscosity of the solution, but also the rheological properties of thesolution. MG can therefore be added to an aqueous liquid to modify itsrheological profile.

Example 17 Effect of Shear Rate on Viscosity of Ethyl PolyAlpha-1,3-Glucan

This Example describes the effect of shear rate on the viscosity of EG.It is shown that EG exhibits shear thinning behavior. Thus, addition ofEG to a liquid can modify the rheological behavior of the liquid.

To prepare a 2 wt % solution of EG, 1 g of EG (DoS 1.03, GeneralMethods) was added to 49 g of DI water. This preparation was thenhomogenized for 15-30 seconds at 20,000 rpm to dissolve the EG. A 1 wt %EG solution was also prepared.

To determine the viscosity of the EG solutions at various shear rates,the EG solutions were subjected to various shear rates using aBrookfield DV III+ Rheometer equipped with a recirculating bath tocontrol temperature (20° C.) and an SC4-21 Thermosel® spindle or ULAspindle and adapter set. The shear rate was increased using a gradientprogram which increased from 10-250 rpm. The shear rate was increased by7.35 (1/s) every 20 seconds for the ULA spindle and adapter, and by 4.9(1/s) every 20 seconds for the SC4-21 spindle. The results of thisexperiment are listed in Table 22.

TABLE 22 Viscosity of EG Solutions at Various Shear Rates ViscosityViscosity Viscosity Viscosity EG (cPs) @ (cPs) @ (cPs) @ (cPs) @ LoadingSpindle 14.72 rpm 66.18 rpm 154.4 rpm 250 rpm 2% ULA 146.76 123.24 N/AN/A 1% ULA 12.76 13.25 12.27 11.90 Viscosity Viscosity ViscosityViscosity (cPs) @ (cPs) @ (cPs) @ (cPs) @ Loading Spindle 10 rpm 83.47rpm 152.0 rpm 232.5 rpm 2% SC4-21 N/A 112.53 105.24 98.8

The results summarized in Table 22 indicate that the viscosity of the EGsolutions is reduced as the shear rate is increased. This observationmeans that EG solutions demonstrate shear thinning behavior.

Thus, EG when dissolved in an aqueous solution not only modifies theviscosity of the solution, but also the rheological properties of thesolution. EG can therefore be added to an aqueous liquid to modify itsrheological profile.

Example 18 Effect of Shear Rate on Viscosity of Hydroxypropyl PolyAlpha-1,3-Glucan

This Example describes the effect of shear rate on the viscosity of HPG.It is shown that HPG exhibits shear thinning behavior. Thus, addition ofHPG to a liquid can modify the rheological behavior of the liquid.

To prepare a 2 wt % solution of the HPG, 1 g of HPG (sample 2, GeneralMethods) was added to 49 g of DI water. This preparation was thenhomogenized for 15-30 seconds at 20,000 rpm to dissolve the HPG.

To determine the viscosity of the HPG solution at various shear rates,the sample was subjected to various shear rates using a Brookfield DVIII+ Rheometer equipped with a recirculating bath to control temperature(20° C.) and a ULA spindle and adapter set. The shear rate was increasedusing a gradient program which increased from 10-250 rpm and the shearrate was increased by 7.35 (1/s) every 20 seconds for the ULA spindleand adapter. The results of the experiment are listed in Table 23.

TABLE 23 Viscosity of HPG Solutions at Various Shear Rates ViscosityViscosity Viscosity Viscosity HPG (cPs) @ (cPs) @ (cPs) @ (cPs) @Loading Spindle 14.72 rpm 66.18 rpm 154.4 rpm 250 rpm 2% ULA 45.73 35.0126.36 20.54

The results summarized in Table 23 indicate that the viscosity of theHPG solution is reduced as the shear rate is increased. This observationmeans that HPG solutions demonstrate shear thinning behavior.

Thus, HPG when dissolved in an aqueous solution not only modifies theviscosity of the solution, but also the rheological properties of thesolution. HPG can therefore be added to an aqueous liquid to modify itsrheological profile.

Example 19 Effect of Shear Rate on Viscosity of Dihydroxypropyl PolyAlpha-1,3-Glucan

This Example describes the effect of shear rate on the viscosity ofdihydroxypropyl poly alpha-1,3-glucan. It is shown that this glucanether exhibits shear thinning behavior. Thus, addition ofdihydroxypropyl poly alpha-1,3-glucan to a liquid can modify therheological behavior of the liquid.

To prepare 2 wt % solutions of dihydroxypropyl poly alpha-1,3-glucan, 1g of either sample 1 or 2 (General Methods) of dihydroxypropyl polyalpha-1,3-glucan was added to 49 g of DI water. Each preparation wasthen homogenized for 12-15 seconds at 20,000 rpm to dissolve the glucanether.

To determine the viscosity of each solution at various shear rates, eachsolution was subjected to various shear rates using a Brookfield DV III+Rheometer equipped with a recirculating bath to hold temperatureconstant at 20° C. The shear rate was increased using a gradient programwhich increased from 10-250 rpm and the shear rate was increased by 4.9(1/s) every 20 seconds. The results of the experiment are listed inTable 24.

TABLE 24 Viscosity of Dihydroxypropyl Poly Alpha-1,3-Glucan Solutions atVarious Shear Rates Viscosity Viscosity Viscosity Viscosity (cPs) @(cPs) @ (cPs) @ (cPs) @ Sample 66.18 rpm 102.9 rpm 183.8 rpm 250 rpm 126.02 25.41 24.02 23.23 2 26.97 25.71 24.61 24.11

The results summarized in Table 24 indicate that the viscosities of thedihydroxypropyl poly alpha-1,3-glucan solutions are reduced as the shearrate is increased. This observation means that this glucan etherdemonstrates shear thinning behavior.

Thus, dihydroxypropyl poly alpha-1,3-glucan when dissolved in an aqueoussolution not only modifies the viscosity of the solution, but also therheological properties of the solution. Such ether derivatives of polyalpha-1,3-glucan can therefore be added to an aqueous liquid to modifyits rheological profile.

Example 20 Effect of Shear Rate on Viscosity of Dihydroxypropyl PolyAlpha-1,3-Glucan Crosslinked with Borate

This Example describes the effect of shear rate on the viscosity ofdihydroxypropyl poly alpha-1,3-glucan when crosslinked with borate. Itis shown that this composition exhibits shear thickening behavior. Thus,addition of borate-crosslinked dihydroxypropyl poly alpha-1,3-glucan toa liquid can modify the rheological behavior of the liquid.

A dihydroxypropyl poly alpha-1,3-glucan sample was first prepared asdescribed in the General Methods. To a prepare a 2 wt % solution of thissample, 1 g of the sample was added to 49 g of DI water. Eachpreparation was then homogenized for 12-15 seconds at 20,000 rpm todissolve the glucan ether.

0.04 g of boric acid was then dissolved in the 2 wt % solution ofdihydroxypropyl poly alpha-1,3-glucan prepared above, including anappropriate amount of added DI water, afterwhich pH was adjusted to 9using 20% sodium hydroxide. This procedure rendered a 0.2 wt % solutionof borate-crosslinked dihydroxypropyl poly alpha-1,3-glucan.

To determine the viscosity of this 0.2 wt % solution at various shearrates, the solution was subjected to various shear rates using aBrookfield DV III+ Rheometer equipped with a recirculating bath to holdtemperature constant at 20° C. The shear rate was increased using agradient program which increased from 10-250 rpm and the shear rate wasincreased by 4.9 (1/s) every 20 seconds. The results of the experimentare listed in Table 25.

TABLE 25 Viscosity of a Borate-Crosslinked Dihydroxypropyl PolyAlpha-1,3-Glucan Solution at Various Shear Rates Viscosity ViscosityViscosity Viscosity (cPs) @ (cPs) @ (cPs) @ (cPs) @ 66.18 rpm 102.9 rpm183.8 rpm 250 rpm 285.35 304.89 407.07 437.6

The results summarized in Table 25 indicate that the viscosity of theborate-crosslinked dihydroxypropyl poly alpha-1,3-glucan solution isincreased as the shear rate is increased. This observation means thatthis crosslinked glucan ether demonstrates shear thickening behavior.This result is in contrast to the results observed with non-crosslinkeddihydroxypropyl poly alpha-1,3-glucan solutions (Example 19), whichexhibited shear thinning behavior.

Thus, borate-crosslinked dihydroxypropyl poly alpha-1,3-glucan whendissolved in an aqueous solution not only modifies the viscosity of thesolution, but also the rheological properties of the solution. Suchcrosslinked ether derivatives of poly alpha-1,3-glucan can therefore beadded to an aqueous liquid to modify its rheological profile.

Example 21 Effect of Shear Rate on Viscosity of Quaternary Ammonium PolyAlpha-1,3-Glucan

This Example describes the effect of shear rate on the viscosity oftrimethylammonium hydroxypropyl poly alpha-1,3-glucan. It is shown thatthis glucan ether derivative exhibits shear thinning behavior. Thus,addition of trimethylammonium hydroxypropyl poly alpha-1,3-glucan to aliquid can modify the rheological behavior of the liquid.

Various samples of trimethylammonium hydroxypropyl poly alpha-1,3-glucanwere prepared as described in the General Methods. To prepare a 2 wt %solution of each sample, 1 g of sample was added to 49 g of DI water.Each preparation was then homogenized for 12-15 seconds at 20,000 rpm todissolve the trimethylammonium hydroxypropyl poly alpha-1,3-glucansample in the water. To determine the viscosity of each 2 wt %quaternary ammonium glucan solution at various shear rates, eachsolution was subjected to various shear rates using a Brookfield DV III+Rheometer equipped with a recirculating bath to control temperature (20°C.) and a ULA (ultra low adapter) spindle and adapter set. The shearrate was increased using a gradient program which increased from 10-250rpm and the shear rate was increased by 4.9 1/s every 20 seconds for theULA spindle and adapter. The results of the experiment are listed inTable 26.

TABLE 26 Viscosity of Quaternary Ammonium Hydroxypropyl PolyAlpha-1,3-Glucan Solutions at Various Shear Rates Viscosity ViscosityViscosity Viscosity (cPs) @ (cPs) @ (cPs) @ (cPs) @ 250 Sample^(a) 66.18rpm 102.9 rpm 183.8 rpm rpm 1A 26.26 24.95 23.42 22.6 1B-1 98.87 83.2270.27 64.43 1B-2 43.76 41.53 38.24 36.57 1B-3 21.53 20.08 19.16 18.721C-1 225.81 158.76 102.02 85.6 1C-2 1246.67 810.93 436.29 334.8 1C-31601.44 992.24 563.95 421.2 1E-1 739.62 493.41 269.67 224 ^(a)Eachsample is described in Table B (General Methods).

The results summarized in Table 26 indicate that the viscosity of eachof the quaternary ammonium poly alpha-1,3-glucan solutions is reduced asthe shear rate is increased. This observation means that these solutionsdemonstrate shear thinning behavior.

Thus, trimethylammonium hydroxypropyl poly alpha-1,3-glucan whendissolved in an aqueous solution not only modifies the viscosity of thesolution, but also the rheological properties of the solution. Thisquaternary ammonium glucan can therefore be added to an aqueous liquidto modify its rheological profile.

What is claimed is:
 1. A composition comprising a cellulase and a polyalpha-1,3-glucan ether compound represented by the structure:

wherein (i) n is at least 6, (ii) each R is independently an H or anorganic group, and (iii) the compound has a degree of substitution ofabout 0.05 to about 3.0.
 2. The composition of claim 1, wherein at leastone organic group is selected from the group consisting of carboxy alkylgroup, hydroxy alkyl group, and alkyl group.
 3. The composition of claim2, wherein at least one organic group is selected from the groupconsisting of carboxymethyl, hydroxypropyl, dihydroxypropyl,hydroxyethyl, methyl, and ethyl group.
 4. The composition of claim 2,wherein the organic group is a carboxymethyl group.
 5. The compositionof claim 1, wherein the composition is in the form of a personal careproduct, household product, or industrial product.
 6. The composition ofclaim 5, wherein the composition is a fabric care product.
 7. Thecomposition of claim 1, wherein the composition is an aqueouscomposition.
 8. The composition of claim 7, wherein the composition hasa viscosity of at least about 10 cPs.
 9. A method for preparing anaqueous composition, the method comprising: contacting an aqueouscomposition with a poly alpha-1,3-glucan ether compound represented bythe structure:

wherein (i) n is at least 6, (ii) each R is independently an H or anorganic group, and (iii) the compound has a degree of substitution ofabout 0.05 to about 3.0; and wherein the aqueous composition prepared insaid method comprises a cellulase.
 10. The method of claim 9, whereinsaid cellulase is: (i) comprised in the aqueous composition prior tosaid contacting step, or (ii) added to the aqueous composition during orafter said contacting step.
 11. The method of claim 9, wherein: (i) theviscosity of the aqueous composition is increased by said polyalpha-1,3-glucan ether compound, and/or (ii) the shear thinning behavioror the shear thickening behavior of the aqueous composition is increasedby said poly alpha-1,3-glucan ether compound.
 12. A method of treating amaterial, said method comprising: contacting a material with an aqueouscomposition comprising a cellulase and a poly alpha-1,3-glucan ethercompound represented by the structure:

wherein (i) n is at least 6, (ii) each R is independently an H or anorganic group, and (iii) the compound has a degree of substitution ofabout 0.05 to about 3.0.
 13. The method of claim 12, wherein thematerial comprises fabric.
 14. The method of claim 13 wherein the fabriccomprises a (i) natural fiber, (ii) synthetic fiber, or a combination ofboth (i) and (ii).
 15. The method of claim 13, wherein the polyalpha-1,3-glucan ether compound adsorbs to the fabric.